Articles formed with renewable and/or sustainable green plastic material and carbohydrate-based polymeric materials lending increased strength and/or biodegradability

ABSTRACT

Described herein are strength characteristics and biodegradation of articles produced using one or more “green” sustainable polymers and one or more carbohydrate-based polymers. A compatibilizer can optionally be included in the article. In some cases, the article can include a film, a bag, a bottle, a cap or lid therefore, a sheet, a box or other container, a plate, a cup, utensils, or the like.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional Application No.62/483,219 filed Apr. 7, 2017. This application is also a continuationin part of U.S. application Ser. No. 14/853,725 filed on Sep. 14, 2015which claims the benefit of U.S. Provisional Patent Application No.62/187,231 filed on Jun. 30, 2015. This application is also acontinuation in part of U.S. application Ser. No. 14/853,780 filed onSep. 14, 2015, and a continuation in part of U.S. application Ser. No.15/481,806 (21132.1) and Ser. No. 15/481,823 (21132.2), both filed onApr. 7, 2017. This application is also a continuation in part of U.S.application Ser. No. 15/691,588 (21132.7) filed on Aug. 30, 2017. Thisapplication also claims the benefit of U.S. Provisional PatentApplication No. 62/440,399 filed on Dec. 29, 2016, and U.S. ProvisionalPatent Application No. 62/442,432 filed on Jan. 4, 2017. The entirecontents of each of the foregoing is incorporated by reference herein.

BACKGROUND

Traditional petrochemical-based plastics are formulated to be strong,lightweight, and durable. However, these plastics are not formed fromrenewable or sustainable resources (e.g., starting materials which canbe renewed within about 100 years or less). The terms renewable andsustainable are used interchangeably herein. Rather, polyethylene (PE),polyethylene terephthalate (PET) and other typical plastics employed inlarge quantities in bottles, bags, and other packaging are made frompetroleum product starting materials, which are not renewable orsustainable.

In an effort to increase sustainability, recently there have been someefforts to develop processes for making such plastic materials fromrenewable source materials, such as sugarcane, corn, or other plantproducts, which plant materials are sustainable. For example, suchrenewable materials may be used to produce ethanol, ethylene glycol, orother chemical building block materials than can be further reacted toproduce monomers which can be polymerized. Such efforts have begun toshow some promise in premium priced products where such “green” plasticresins may be blended with conventional petrochemical-based resins(e.g., to produce a bottle or other packaging in which a fraction (e.g.,30%) of the materials are sustainable. In fact, some products may now bemade from 100% “green” plastic resins.

While blends of such “green” materials and conventional petro-chemicalplastics have begun to become available, there are still practicaldifficulties in replacing the remaining conventional petro-chemicalplastic materials with all sustainable materials, in terms of challengesin processing, cost, and other considerations.

In addition, even while reducing use of conventional non-sustainableplastic materials through substitution of some of the material withsustainable plastic materials, the resulting plastic packaging is stillnot biodegradable. For example, even a plastic package made from 100%“green” plastic or including a fraction of “green” PE or green “PET” isnot biodegradable. Such lack of biodegradability presents an enormouscontinuing problem. For example, hundreds of millions of tons ofnon-biodegradable plastic sits in landfills or floats in the ocean, evenif a portion of such plastic were sourced from sustainable materials. Itwould be a significant advance in the art if articles could be providedwhich were biodegradable. Increased strength would also be desirable. Itwould be a further advance if such an article were entirely formed fromsustainable materials.

SUMMARY

This disclosure is directed to articles that are formed with renewableor sustainable “green” plastic materials and carbohydrate-based (e.g.,starch-based) polymeric materials, which lend at least one of increasedstrength and/or biodegradability to the resulting blended material. Forexample, an embodiment is directed to an article comprising acarbohydrate-based (e.g., starch-based) polymeric material configured toprovide other materials of the article with biodegrability, and asustainable polymeric material sourced from sustainable plant sources(e.g., sugarcane, corn, or the like). In an embodiment, the sustainablepolymeric material may be processed into a polymer that otherwiseexhibits similar if not identical characteristics to a petro-chemicalbased polymer (e.g., it may be “green” polyethylene, “green”polypropylene, “green” polyethylene terephthalate (PET), or the like).Such a “green” polymer may have similar if not identical chemical andphysical properties as compared to the same polymer (e.g., polyethylene)formed from a petro-chemical feedstock. The carbohydrate-based polymericmaterial may actually lend biodegradability characteristics to thesustainable polymeric material with which it is blended or otherwiseformed, where such sustainable polymeric material may not otherwiseexhibit such biodegradability characteristics (or such characteristicsmay be enhanced, if the sustainable polymeric material already didexhibit some biodegradability). For example, an amount of the articlethat biodegrades within 5 years under simulated landfill conditions(e.g., under any typical ASTM standard such as, but not limited toD-5511 and/or D-5526), simulated industrial compost conditions (such asASTM D-5338), or simulated marine conditions (such as ASTM D-6691) isgreater than the included amount of the carbohydrate-based polymericmaterial.

In other words, if the article is formed from a blend including 25% ofthe carbohydrate-based polymeric material, the amount of the articlethat biodegrades under such conditions is greater than 25% (i.e., someof the sustainable polymeric material is also degrading, even thoughsuch sustainable polymeric material may not degrade under similarconditions on its own).

Test results obtained by Applicant show that such degradation can occurrelatively rapidly, e.g., sometimes within about 180 days (6 months),within about 1 year, within about 2 years, or within about 3 years.

In addition or alternative to biodegradability, such articles mayexhibit increased strength as compared to otherwise similar articles,but formed within inclusion of the carbohydrate-based polymericmaterial. For example, an embodiment is directed to an article includingone or more carbohydrate-based polymeric materials (e.g., such as thosedescribed above), and one or more sustainable polymeric materialssourced from sustainable plant sources, wherein a strength of thearticle is at least 5% greater than the article would have if madewithout the carbohydrate-based polymeric material. For example, thepresent inventors have discovered that inclusion of such acarbohydrate-based polymeric material in the article (e.g., as a blendof the two polymeric materials) can provide increased strength, ascompared to what the sustainable polymeric material alone would provide.

These and other advantages and features of the present invention willbecome more fully apparent from the following description and appendedclaims, or may be learned by the practice of the invention as set forthhereinafter.

BRIEF DESCRIPTION OF THE DRAWINGS

In order that the manner in which the above-recited and other advantagesand objects of the invention are obtained, a more particular descriptionof the invention briefly described above will be rendered by referenceto specific embodiments thereof which are illustrated in the appendeddrawings. Understanding that these drawings depict only typicalembodiments of the invention and are not therefore to be considered tobe limiting of its scope, the invention will be described and explainedwith additional specificity and detail through the use of theaccompanying drawings in which:

FIG. 1 illustrates a flow diagram of an example process of forming anarticle including biodegradable materials.

FIG. 2 illustrates components of an example manufacturing system toproduce articles including biodegradable materials.

FIG. 3 shows elastic modulus and elongation at break data for variouspetrochemical plastics that are typically neither biodegradable norcompostable (labeled standard plastics) as well as various plastics thatare more “environmentally friendly” in one or more aspects.

FIG. 4 shows X-ray diffraction patterns for an exemplary “ESR”carbohydrate-based polymeric material commercially available fromBiologiQ as compared to that of the blend of native corn starch andnative potato starch used to form the ESR.

FIG. 5 shows dart strength for different thickness films based onpercentage of carbohydrate-based polymeric material in the film.

FIG. 6 shows dart strength for different thickness films (from about 0.1mil up to 2 mils) formed from a blend of 25% carbohydrate-basedpolymeric material, about 5% compatibilizer, and about 70% PE, ascompared to 100% PE film, and also showing comparison for existingproduce bags, haul out bags, and potato bags.

FIG. 7 shows dart strength for different thickness films for variousblended films including ESR, as well as comparative films formed fromvirgin or recycled materials.

FIG. 8A and FIG. 8B illustrate percent biodegradation measured over 32days according to biomethane potential testing of four samples formedaccording to techniques described herein.

FIG. 9A and FIG. 9B illustrate percent biodegradation measured over 32days according to biomethane potential testing of three additionalsamples formed according to techniques described herein.

FIG. 10A and FIG. 10B illustrate percent biodegradation measured over 91days according to biomethane potential testing of four samples formedaccording to techniques described herein.

FIG. 11A and FIG. 11B illustrate percent biodegradation measured over 91days according to biomethane potential testing of three additionalsamples formed according to techniques described herein.

FIG. 12A and FIG. 12B illustrate percent biodegradation measured over 71days according to biomethane potential testing of one sample formedaccording to techniques described herein.

FIG. 13A and FIG. 13B show the results of the biodegradation portion ofthe ASTM D-6400 test performed according to ASTM D-5338 for a firstsample and a second sample formed according to techniques describedherein.

FIG. 14A and FIG. 14B show the results of the biodegradation portion ofthe ASTM D-6400 test performed according to ASTM D-5338 for a thirdsample and a fourth sample formed according to techniques describedherein.

FIG. 15 shows percent biodegradation measured over 349 days according totesting conducted under ASTM D-5511 for three samples formed accordingto the present disclosure.

FIG. 16 shows percent biodegradation measured over 843 days according totesting conducted under ASTM D-5526 for potato bags made with 25% ESR,70% PE, and 5% compatibilizer under simulated landfill conditions.

FIG. 17 shows percent biodegradation measured over 370 days according totesting conducted under ASTM D-5338 for various samples made accordingto the present disclosure, as well as comparative controls.

FIG. 18 shows percent biodegradation measured over 205 days according toASTM D-6691, meant to simulate marine conditions, for various samplesmade according to the present disclosure, as well as comparativecontrols.

FIG. 19A shows dart strength for films made with a blend of ESRcarbohydrate-based polymeric material and a biopolyethylene or “green”PE. Dart strength is shown as a function of ESR percentage, for films ofvarious thicknesses.

FIG. 19B presents similar data as FIG. 19A, but shows dart strength as afunction of film thickness, for blends including varying percentages ofESR.

DETAILED DESCRIPTION I. Definitions

All publications, patents and patent applications cited herein, whethersupra or infra, are hereby incorporated by reference in their entiretyto the same extent as if each individual publication, patent or patentapplication was specifically and individually indicated to beincorporated by reference.

The term “comprising” which is synonymous with “including,”“containing,” or “characterized by,” is inclusive or open-ended and doesnot exclude additional, unrecited elements or method steps.

The term “consisting essentially of” limits the scope of a claim to thespecified materials or steps “and those that do not materially affectthe basic and novel characteristic(s)” of the claimed invention.

The term “consisting of” as used herein, excludes any element, step, oringredient not specified in the claim.

The terms “a,” “an,” “the” and similar referents used in the context ofdescribing the inventive features (especially in the context of thefollowing claims) are to be construed to cover both the singular and theplural, unless otherwise indicated herein or clearly contradicted bycontext. Thus, for example, reference to a “starch” can include one, twoor more starches.

“Film,” as used herein, refers to a thin continuous article thatincludes one or more polymeric materials that can be used to separateareas or volumes, to hold items, to act as a barrier, and/or as aprintable surface.

“Bag,” as used herein, refers to a container made of a relatively thin,flexible film that can be used for containing and/or transporting goods.

“Bottle,” as used herein, refers to a container that can be made fromthe presently disclosed plastics, typically of a thickness greater thana film, and which typically includes a relatively narrow neck adjacentan opening. Such bottles may be used to hold a wide variety of products(e.g., beverages, personal care products such as shampoo, conditioner,lotion, soap, cleaners, and the like).

Unless otherwise stated, all percentages, ratios, parts, and amountsused and described herein are by weight.

Numbers, percentages, ratios, or other values stated herein may includethat value, and also other values that are about or approximately thestated value, as would be appreciated by one of ordinary skill in theart. A stated value should therefore be interpreted broadly enough toencompass values that are at least close enough to the stated value toperform a desired function or achieve a desired result, and/or valuesthat round to the stated value. The stated values include at least thevariation to be expected in a typical manufacturing process, and mayinclude values that are within 25%, 15%, 10%, within 5%, within 1%, etc.of a stated value. Furthermore, the terms “substantially”, “similarly”,“about” or “approximately” as used herein represent an amount or stateclose to the stated amount or state that still performs a desiredfunction or achieves a desired result. For example, the term“substantially” “about” or “approximately” may refer to an amount thatis within 25% of, within 15% of, within 10% of, within 5% of, or within1% of, a stated amount or value.

Some ranges are disclosed herein. Additional ranges may be definedbetween any values disclosed herein as being exemplary of a particularparameter. All such ranges are contemplated and within the scope of thepresent disclosure. Further, recitation of ranges of values herein isintended to serve as a shorthand method of referring individually toeach separate value falling within the range. Unless otherwise indicatedherein, each individual value is incorporated into the specification asif it were individually recited herein.

All numbers expressing quantities of ingredients, constituents,conditions, and so forth used in the specification and claims are to beunderstood as being modified in all instances by the term “about”.Notwithstanding that the numerical ranges and parameters setting forththe broad scope of the invention are approximations, the numericalvalues set forth in the specific examples are reported as precisely aspossible. Any numerical value, however, inherently contains certainerrors necessarily resulting from the standard deviation found in theirrespective testing measurements.

The phrase ‘free of’ or similar phrases as used herein means that thecomposition comprises 0% of the stated component, that is, the componenthas not been intentionally added to the composition. However, it will beappreciated that such components may incidentally form under appropriatecircumstances, may be incidentally present within another includedcomponent, e.g., as an incidental contaminant, or the like.

The phrase ‘substantially free of’ or similar phrases as used hereinmeans that the composition preferably comprises 0% of the statedcomponent, although it will be appreciated that very smallconcentrations may possibly be present, e.g., through incidentalformation, incidental contamination, or even by intentional addition.Such components may be present, if at all, in amounts of less than 1%,less than 0.5%, less than 0.25%, less than 0.1%, less than 0.05%, lessthan 0.01%, less than 0.005%, or less than 0.001%.

II. Introduction

The present disclosure is directed to, among other things, articles thatare formed from blends of polymeric materials, including a sustainablepolymeric material formed from plant sources, as well as acarbohydrate-based (e.g., starch-based) polymeric material. A smallamount of compatibilizer may also be present, such that all orsubstantially all of the polymeric content of the article can be formedfrom polymers sourced from plant sources. Such characteristic isparticularly advantageous, from a sustainability perspective.

In addition to desirable sustainability characteristics, thecarbohydrate-based polymeric material may be configured to provide thematerial with which it is blended (the “green” sustainable polymericmaterial, such as “green” PE (or biopolyethylene), “green” PP, orBioPET) with biodegradability. In other words, even where the “green”sustainable polymeric material is not alone itself biodegradable, itsinclusion in the article which also includes the carbohydrate-basedpolymeric material can actually result in its becoming biodegradable.Such a result is also of great advantage.

In addition, many articles (e.g., particularly thin films) do not haveparticularly good strength when formed from conventional plasticmaterials (e.g., petrochemical-based polymeric materials), such thatincreased strength at a given thickness would be desirable. Because“green” plastic materials exhibit physical characteristics that aresimilar to their corresponding conventional petrochemical-based cousins,such “green” plastic materials also do not have particularly goodstrength, and a means for increasing strength, without increasingarticle thickness would be desirable. When blended withcarbohydrate-based polymeric materials as described herein, suchincreased strength results are achieved. For example, while apolyethylene film (e.g., either biopolyethylene (“green” PE) ormetallocene petrochemical-based PE) may have a dart impact strength ofabout 150 g for a 1 mil thick film, it would be advantageous if thestrength could be increased, without increasing film thickness. Thepresent embodiments can provide such increased strength. For example,upon blending with a carbohydrate-based polymeric material as describedherein, strength may increase by at least 5%. Typical results of someembodiments may result in strength increases of 20% or even more.

The articles can be produced by mixing the carbohydrate-based polymericmaterial and the sustainable polymeric material, heating the mixture,and molding (e.g., injection molding) the mixture, extruding themixture, blow molding the mixture, thermoforming the mixture, or thelike. Various other plastic manufacturing processes will be apparent tothose of skill in the art in light of the present disclosure.

The articles described herein can be produced in the form of anyconceivable structure, including, but not limited to bottles, boxes,other containers, sheets, films, bags, and the like. Thin films for bagsand film wraps (e.g., for wrapping around or over a product) can easilybe made using blown film equipment.

Examples of suitable carbohydrate-based or starch-based polymericmaterials for use in forming such articles are available from BiologiQ,under the tradename ESR (“Eco Starch Resin” or “Eco Sustainable Resin”).Specific examples include, but are not limited to GS-270, GS-300, andGS-330. Specific characteristics of such ESR materials will be describedin further detail herein. Other carbohydrate-based or starch-basedpolymeric materials may also be suitable for use, such that ESRavailable from BiologiQ is merely a non-limiting example of a suitablecarbohydrate-based or starch based polymeric material. Thermoplasticstarch (TPS) materials available from other suppliers that may provideone or more desirable characteristics as described herein mayalternatively or additionally be used.

III. Exemplary Articles and Methods

The techniques and processes described herein can be implemented in anumber of ways. Example implementations are provided below withreference to the following figures.

FIG. 1 illustrates an exemplary process 100 for manufacturing an articleaccording to the present invention. At 102, the process 100 can includeproviding one or more sustainable polymeric materials (e.g.,biopolyethylene (“green” PE), “green” PP, bioPET or the like). At 104,the process 100 can include providing one or more carbohydrate-basedpolymeric materials. In some cases, the one or more carbohydrate-basedpolymeric materials can include one or more starch-based polymericmaterials. The one or more carbohydrate-based polymeric materials andthe one or more sustainable polymeric materials can be provided in anyparticular form, such as pellets, powders, nurdles, slurry, and/orliquids. In some embodiments, pellets can be used.

In addition, providing the one or more sustainable polymeric materialsand the one or more carbohydrate-based polymeric materials can includefeeding the one or more sustainable polymeric materials and the one ormore carbohydrate-based polymeric materials into an extruder. Forexample, the polymeric materials can be fed into one or more hoppers ofan extruder. The polymeric materials can be fed into the extruder intothe same chamber, into different chambers, at approximately the sametime (e.g., through the same hopper), or at different times (e.g.,through different hoppers, one being introduced into the extruderearlier on along the screw than the other). It will be apparent thatmany various possibilities may be suitable.

In some cases, the sustainable polymeric material can include apolyolefin. For example, the sustainable polymeric materials caninclude, but are not limited to, a “green” polyethylene (bioPE), a“green” polypropylene (bioPP), a bioPET, or other plastic material thatcan be formed from sustainable plant sources. By way of non-limitingexample, “green” PE can be derived from ethanol that may be formed fromsugarcane, other sugar crops (e.g., sugar beets) or a grain (e.g., corn,wheat, or the like). “Green” PE (also sometimes referred to as “bioPE”has a similar chemical structure as PE formed from a petrochemicalfeedstock, but in which the ethanol, or the ethylene monomer used inpolymerization is derived from sustainable sources, rather than apetrochemical feedstock. “Green” PP could similarly be formed frompropylene that may be derived from propanol (or perhaps isopropanol)derived from sugarcane, other sugar crops, or grains (e.g., corn).Another example of a “green” sustainable polymeric material is bioPET,e.g., where the monomers used in forming the poly(ethyleneterephthalate) (e.g., typically ethylene glycol and terephthalic acid)may similarly be derived from plant sources such as sugarcane, othersugar crops, or grains. PET is the most common thermoplastic resin ofthe polyester family. Another polyester that could similarly be formedfrom sustainable plant sources is polybutyrate adipate terephthalate(bioPBAT). PBAT can be formed as a copolyester of adipic acid, 1,4butanediol and dimethyl terephthalate. One or more of such startingmaterials can be derived from sustainable plant sources. Anotherpossible “green” polymeric resin material that may be used ispoly(lactic acid). PLA is typically produced from monomers of lacticacid and/or lactide esters, as will be appreciated by those of skill inthe art. One or more starting materials for PLA production could bederived from sustainable plant sources. Other possible “green polymersthat will be familiar to those of skill in the art that could be usedinclude PBS (polybutylene succinate) or PCL (polycaprolactone). Those ofskill in the art will be familiar with processes for synthesizing suchpolymers. One or more of the components used for manufacture of suchpolymers could be derived from a suitable renewable plant or otherrenewable biological source (e.g., bacterial generation). “Green” PE isavailable from Braskem, bioPET is available from and used in CocaCola™'s Plant Bottle and likely from other plastics manufacturers aswell. While PE, PP, PET and PBAT are examples of “green” bioplasticsthat may be formed from materials derived from sustainable plantsources, it will be appreciated that numerous other “green” plastics mayalso be suitable for use, so long as they can be formed at least in partfrom sustainable materials (e.g., plant sources). In addition, whilesugarcane, other sugar crops, corn, wheat and other grains may beexemplary nonlimiting examples of plant materials from which such“green” polymeric materials can be derived, it will be appreciated thatnumerous other plants and materials may also suitably be used.

The carbohydrate-based polymeric materials can be formed from aplurality of materials (e.g., a mixture) including one or more starches.For example, the one or more starches can be produced from one or moreplants, such as corn starch, tapioca starch, cassava starch, wheatstarch, potato starch, rice starch, sorghum starch, and the like. Insome embodiments, a mixture of different types of starches may be used,which Applicant has found to result in a synergistic increase instrength. A plasticizer is also present within the mixture of componentsfrom which the carbohydrate-based polymeric materials are formed. Watermay also be used in forming the carbohydrate-based polymeric material,although only a small to negligible amount of water is present in thefinished carbohydrate-based polymeric material.

It will be appreciated that in some embodiments then, the entirepolymeric content (or substantially the entire polymeric content) of thearticle may be derived from plant materials. While the “green” polymericmaterial typically employs polymerizable monomers or other smallmolecule polymerizable components that may be derived from ethanol (orthe like) formed from a desired plant material, the carbohydrate-based(or starch-based) polymeric material may be formed from starch (andglycerin or another plasticizer), rather than processing such starch orother plant materials to form smaller polymerizable monomers. Thus, themolecular weight of the starch(es) used to make the starch-basedpolymeric material may typically be orders of magnitude greater than themolecular weight of the relatively small molecule monomers produced foruse in making the “green” sustainable polymeric material. For example,the plant sourced monomers or other polymerizable components used inmaking the “green” sustainable polymeric material may typically be lessthan about 500 Daltons, less than 400 Daltons, less than 300 Daltons,less than 200 Daltons, or less than 100 Daltons, while the molecularweight of the starch(es) used in making the starch-based polymericmaterial may typically be significantly higher, often more than 500Daltons, often measured in thousands, tens of thousands, or even higher(e.g., more than 500 Daltons, at least 1000 Daltons, at least 10,000Daltons, at least 25,000 Daltons, at least 40,000 Daltons, or the like).In other words, the starch materials (e.g., native starches) used informing the starch-based material are typically more complex moleculesthan the monomers or other polymerizable components used in making the“green” sustainable polymeric material. For example, corn starch mayhave a molecular weight of about 693 Daltons. Potato starch may have amolecular weight that may vary widely, e.g., from about 20,000 Daltonsto about 400 million Daltons (e.g., amylose may range from about 20,000Daltons to about 2 million Daltons, while amylopectin may range fromabout 65,000 Daltons to about 400 million Daltons). Tapioca starch mayhave a molecular weight ranging from about 40,000 Daltons to about340,000 Daltons. The glycerin employed in forming the starch-basedpolymeric material may also be derived from sustainable sources.Glycerin of course has a molecular weight of 92 Daltons.

The one or more carbohydrate-based polymeric materials can be formedfrom mostly starch. For example, at least 65%, at least 70%, at least75%, or at least 80% by weight of the carbohydrate-based polymericmaterial may be attributable to the one or more starches. In anembodiment, from 65% to 90% by weight of the finished carbohydrate-basedpolymeric material may be attributed to the one or more starches. Otherthan negligible water content, the balance of the finishedcarbohydrate-based polymeric material may be attributed to theplasticizer (e.g., glycerin). The percentages above may represent starchpercentage relative to the starting materials from which thecarbohydrate-based polymeric material is formed, or that fraction of thefinished carbohydrate-based polymeric material that is derived from orattributable to the plasticizer (e.g., at least 65% of the carbohydratebased polymeric material may be attributed to (formed from) thestarch(es) as a starting material). Although some water may be used informing the carbohydrate-based polymeric material, substantially thebalance of the carbohydrate-based polymeric material may be attributedto glycerin, or another plasticizer. Very little residual water (e.g.,less than 2%, typically no more than about 1%) may be present in thefinished carbohydrate-based polymeric material.

For example, the materials from which the one or more carbohydrate-basedpolymeric materials are formed can include at least 12%, at least 15%,at least 18%, at least 20%, at least 22%, no greater than 35%, nogreater than 32%, no greater than 30%, no greater than 28%, or nogreater than 25% by weight of a plasticizer. Such percentages mayrepresent that fraction of the finished carbohydrate-based polymericmaterial that is derived from or attributable to the plasticizer (e.g.,at least 12% of the carbohydrate based polymeric material may beattributed to (formed from) the plasticizer as a starting material).

Exemplary plasticizers include, but are not limited to glycerin,polyethylene glycol, sorbitol, polyhydric alcohol plasticizers, hydrogenbond forming organic compounds which do not have a hydroxyl group,anhydrides of sugar alcohols, animal proteins, vegetable proteins,aliphatic acids, phthalate esters, dimethyl and diethylsuccinate andrelated esters, glycerol triacetate, glycerol mono and diacetates,glycerol mono, di, and tripropionates, butanoates, tearates, lactic acidesters, citric acid esters, adipic acid esters, stearic acid esters,oleic acid esters, other acid esters, or combinations thereof. Glyerinmay be preferred.

The finished carbohydrate-based polymeric material may include nogreater than 5%, no greater than 4%, no greater than 3%, no greater than2%, no greater than 1.5%, no greater than 1.4%, no greater than 1.3%, nogreater than 1.2%, no greater than 1.1%, or no greater than 1% by weightwater. The ESR materials available from BiologiQ are examples of suchfinished carbohydrate-based polymeric materials, although it will beappreciated that other materials available elsewhere (e.g., at somefuture time) may also be suitable for use.

In some embodiments, mixtures of different starches may be used informing the carbohydrate-based polymeric material. Use of such a mixtureof different starches (e.g., coming from different plants) has beenfound to surprisingly be associated with a synergistic increase instrength in articles including such carbohydrate-based polymericmaterials. In such a mixture of starches, a starch can be present in themixture in an amount of at least 1%, at least 2%, at least 3%, at least4%, at least 5%, at least 10%, at least 15%, at least 20%, at least 25%,at least 30%, at least 35%, at least 40%, no greater than 95%, nogreater than 90%, no greater than 85%, no greater than 80%, no greaterthan 75%, no greater than 70%, no greater than 65%, no greater than 60%,no greater than 55%, no greater than 50%, or from 10% to 50% by weightrelative to the combined weight of the plurality of starches. Somenon-limiting exemplary mixtures may include 90% of a first starch, and10% of a second starch, or 30% of a first starch and 70% of a secondstarch, or 50% of a first starch and 50% of a second starch. Mixtures ofmore than two starches (e.g., using 3 or 4 different starches) can alsobe used.

Examples of suitable carbohydrate-based (e.g., starch-based) polymericmaterials for use in forming films and other articles are available fromBiologiQ, located in Idaho Falls, Id., under the tradename ESR (“EcoStarch Resin”). Specific examples include, but are not limited toGS-270, GS-300, and GS-330. Additional details relative to fractions ofstarch and glycerin or other plasticizers used in forming ESR aredescribed in Applicant's other patent applications, already incorporatedherein by reference. ESR may be provided in pellet form. Physicalcharacteristics for GS-270 and GS-300 are shown in Table 1 below.

TABLE 1 GS-270 GS-300 TEST NOMINAL NOMINAL PROPERTY METHOD VALUE VALUEDensity ASTM D-792 1.40 g/cm³ 1.42 g/cm³ THERMAL PROPERTIES Melt FlowIndex ASTM D-1238 1.98 g/10 min 1.95 g/10 min 200° C./5 kg Melting Temp.ASTM D-3418 166-180° C. 166-180° C. Range Glass Transition ASTM D-341881-100° C. 81-100° C. Temp. MECHANICAL PROPERTIES Tensile Strength ASTMD-638 >30 MPa >14 MPa @ Yield Tensile Strength ASTM D-638 >30 MPa >14MPa @ Break Young's Modulus ASTM D-638 1.5 GPa 1.5 GPa Elongation atASTM D-638 <10% <10% Break Impact Resistance ASTM D-5628 3.5 kg 4.5 kg(Dart) ADDITIONAL PROPERTIES Water Content ASTM D-6980 ≤1.5%, or ≤1%≤1.5%, or ≤1%

The above characteristics shown for GS-270 and GS-300 are exemplary ofother ESR products available from BiologiQ, although values may varysomewhat. For example, ESR products from BiologiQ may generally have aglass transition temperature ranging from about 70° C. to about 100° C.Those of skill in the art will appreciate that glass transitiontemperature can be indicative of degree of crystallinity. Values formelting temperature range, density, Young's Modulus, and water contentmay be identical or similar to those shown above in Table 1. Somecharacteristics may similarly vary somewhat (e.g., ±25%, or ±10%) fromvalues shown for GS-270 and GS-300. ESR has an amorphous structure(e.g., more amorphous than typical raw starch). For example, typical rawstarch powder has a mostly crystalline structure (e.g., greater than50%), while ESR has a mostly amorphous structure (e.g., less than 10%crystalline).

ESR has a low water content, as described. As ESR absorbs moisture, itexhibits plastic behavior and becomes flexible. When removed from ahumid environment, the material dries out and becomes stiff again (e.g.,again exhibiting less than about 1% water content). The moisture presentin ESR (e.g., in pellet form) may be released in the form of steamduring processing such as that shown in FIG. 1. As a result, films orother articles produced from a starch-based polymeric material such asESR blended with a sustainable polymeric material may exhibit even lowerwater content, as the sustainable polymeric material typically willinclude no or negligible water, and the water in the ESR may typicallybe released during manufacture of a desired article.

Such low water content in the carbohydrate-based polymeric material canbe important, as significant water content can result in incompatibilitywith the sustainable polymeric material, particularly if the articlerequires formation of a thin film. For example, as the water vaporizes,this can result in voids within the film or other article, as well asother problems. When blowing a thin film, the carbohydrate-basedpolymeric material used may preferably include no more than about 1%water.

Low water content is not achieved in the ESR material throughesterification, as is common in some conventional TPS materials that mayinclude relatively low water content. Such esterification can beexpensive and complex to perform. Furthermore, the ESR materials thatare exemplary of the carbohydrate-based polymeric materials employableherein also typically do not themselves actually include anyidentifiable starch, or identifiable glycerin, as such, as the startingmaterials of the ESR or other carbohydrate-based polymeric material havebeen chemically reacted and/or altered. X-ray diffraction patterns ofexemplary carbohydrate-based polymeric materials as described below(e.g., and shown in FIG. 4) evidence such chemical alteration, showingthat the finished polymeric material may be substantially devoid ofstarch in such identifiable, native form. In other words, thecarbohydrate-based polymeric material is not simply recognized as amixture including starch and glycerin. The low water content achievablein the carbohydrate-based polymeric material is believed to be due atleast in part to the chemical alteration of the starch and plasticizermaterials into a thermoplastic polymer, which does not retain water aswould native starch, or conventional thermoplastic starches.

Returning to FIG. 1, processing at relatively high temperatures mayresult in some release of volatized glycerin (e.g., visible as smoke).If needed (e.g., where stored pellets may have absorbed additionalwater), drying of pellets can be performed by simply introducing warmdry air, e.g., at 60° C. for 1-4 hours, which is sufficient to drive offany absorbed water. Pellets should be dried to less than about 1%moisture content prior to processing, particularly if forming a film.ESR pellets may simply be stored in a sealed container with a desiccantin a dry location, away from heat to minimize water absorption, and toprevent undesired degradation.

In addition to ESR being thermoplastic, the ESR may also be thixotropic,meaning that the material is solid at ambient temperature, but flows asa liquid when heat, pressure and/or frictional movement are applied.Advantageously, pellets of ESR can be used the same as petrochemicalbased pellets (or “green” plastic pellets) in standard plasticproduction processes. ESR materials and products made therefrom mayexhibit gas barrier characteristics. Products (e.g., films) made usingsuch ESR pellets exhibit oxygen gas barrier characteristics (e.g., seeExample 5 for specific exemplary results). ESR materials may benon-toxic and edible, made using raw materials that are all edible. ESRand products made therefrom may be water resistant, but water soluble.For example, ESR may resist swelling under moist heated conditions tothe point that pellets (e.g. with a size of 3-4 mm) thereof may notcompletely dissolve in boiling water within 5 minutes, but a pellet willdissolve in the mouth within about 10 minutes. ESR may be stable, inthat it may not exhibit any significant retrogradation, even if left inrelatively high humidity conditions, which characteristic differs frommany other thermoplastic starch materials. Of course, products made withESR may also exhibit such characteristics. If ESR is stored in humidconditions, the excess absorbed water can simply be evaporated away, andonce the water content is no more than about 1%, it can be used informing a film or other article.

The ESR material also does not typically undergo biodegradation undertypical storage conditions, even in relatively humid conditions, as theother conditions typical of a landfill, compost or similar disposalenvironment containing the particular needed microorganisms are notpresent. Of course, where such conditions are present, not only does theESR biodegrade, but otherwise non-biodegradable sustainable polymericmaterials blended therewith surprisingly also biodegrade.

ESR can be cost competitive, being manufactured at a cost that iscompetitive with traditional polyethylene plastic resins. ESR can bemixed with other (e.g., “green” or even petrochemical-based) polymers,including, but not limited to PE, PP, PET, PBAT, PLA, or others. In someembodiments, the ESR could be provided in a masterbatch formulation thatmay include the starch-based polymeric material as described above, andan amount of one or more compatibilizers. The masterbatch may alsoinclude one or more “green” polymeric materials, and/or even one or morepetrochemical-based polymeric materials, if such were desired. Suchmasterbatch formulation pellets could be mixed with pellets of the“green” sustainable polymeric material at the time of processing. Anyconceivable ratios may be used in mixing such different pellets,depending on the desired percentage of ESR and/or compatibilizer and/or“green” sustainable polymeric material in the finished article.

ESR includes very low water content. For example, although raw starch(e.g., used in forming ESR) may typically include about 13% water byweight, the finished ESR pellets available from BiologiQ include lessthan about 1% water. ESR materials are biodegradable, and as describedherein, not only is the starch-based ESR material biodegradable, butwhen blended with other polymers, such as “green” polyethylene, bioPET,bioPBAT, or the like, which may not be biodegradable, the blendedmaterial becomes substantially entirely biodegradable. Such results arequite surprising, and particularly advantageous. The Examples hereinevidence such surprising results. Applicant is not aware of any typicalthermoplastic starch materials that claim to, or are capable ofproviding such characteristics when blended with other polymers.

The ESR material may exhibit some elasticity, although its elasticitymay be less than many other polymers (e.g., particularly “green”sustainable polymers that mimic their petrochemical-based polymercousins). Films and other articles may be formed from blends of ESR andany desired “green” sustainable polymer(s), providing elasticity resultsexhibiting increased strength, at a given article thickness. While filmsare described and often used in the Examples herein, where strength isoften of critical importance, it will be apparent that increasedstrength can also be provided in articles other than films (e.g.,bottles, sheets, boxes, or other forms). Table 2 below shows elongationat break and elastic modulus values for various standard plastic (“SP”)materials, various “environmentally-friendly” plastic materials, andESR, for comparison. By “environmentally friendly”, the material mayhave one or more environmentally desirable characteristics, such as itsbeing at least partially derived from a sustainable material, beingcompostable, and/or being biodegradable. The ESR in Table 2 had atensile strength of 40 MPa.

TABLE 2 ENVIRONMENTALLY FRIENDLY OR ELONGATION ELASTIC MATERIAL STANDARDPLASTIC AT BREAK MODULUS EcoFlex EP 700% 0.10 GPa C1200 ESR EP 100%  1.5GPa HDPE SP 650% 0.80 GPa LDPE SP 550% 0.40 GPa PBS EP 450% 0.50 GPa PCLEP 600% 0.20 GPa PHA EP 300% 3.40 GPa PLA EP 150% 3.50 GPa PET SP 200%2.50 GPa PP SP 500% 1.75 GPa ABS SP  25% 2.00 GPa Nylon SP 100% 3.00 GPa

FIG. 3 shows similar data as in Table 2, in chart form. Of course, someof the products listed in the table and shown in FIG. 3 that are listedas standard plastics have “green” cousins that can be derived fromsustainable sources, such as, but not limited to, BioPET, “green” PP,“green” PE, and bioPBAT. PLA is compostable, meaning that it can degradeunder elevated temperature conditions (i.e., composting conditions), butis technically not “biodegradable”. The other exemplary materials listedabove such as EcoFlex, PBS, PCL, PHA may be both biodegradable andcompostable. FTC Green guidelines stipulate that a plastic cannot makean unqualified claim that it is “degradable” unless it will degradewithin a “reasonably short period of time” (most recently defined aswithin 5 years) “after customary disposal”.

The ESR materials described as suitable for use herein as thecarbohydrate-based (e.g., starch-based) polymeric material aresubstantially amorphous. For example, raw starch powder (e.g., such asis used in making ESR and various other thermoplastic starch materials)has approximately a 50% crystalline structure. ESR materials availablefrom BiologiQ differ from many other commercially availablethermoplastic starch (TPS) materials in crystallinity versus amorphouscharacteristics. For example, p. 62-63 of “Thermoplastic StarchComposites and Blends” a PhD thesis by Kris Frost (September 2010)states “[o]f particular interest in TPS is completeness ofgelatinisation during processing, and any subsequent tendency towardretrogradation to form V-type amylose crystals”. Frost further continues“[g]elatinisation involves loss of granular and crystalline structuresby heating with water and often including other plasticizers ormodifying polymers. Retrogradation is due to the re-coiling of amylosehelical coils. Starch molecules disrupted during gelatinisation slowlyre-coil into their native helical arrangements or new single helicalconformations known as V type, causing TPS films to rapidly becomebrittle and lose optical clarity”. Thus, conventional TPS tends tore-form a crystalline structure after the gelatinization process used toproduce the TPS from raw starch. On the contrary, the ESR materialavailable from BiologiQ does not re-form a crystalline structure anddoes not become brittle. It remains flexible. In addition, it canmaintain a stable, high degree of optical clarity, so as to be useful informing relatively optically clear films (e.g., particularly bysandwiching ESR between polyethylene or other polyolefin layers).

In contrast to typical TPS materials, the ESR materials that aresuitable examples of starch-based polymeric materials for use in formingarticles described in the present application have an amorphousmicrostructure, and physical characteristics as shown in Table 1. Thedifference in the molecular structure between conventional TPS and ESRmaterials is evidenced by the ESR materials as described herein beingmuch less crystalline than conventional thermoplastic starch-basedmaterials as shown by X-ray diffraction, shown in FIG. 4, comparing FTIRdiffraction pattern results for ESR material available from BiologiQ(sample 1) as compared to a blend of native raw corn starch and nativeraw potato starch, from which the ESR in FIG. 4 was formed. Thediffraction pattern of the ESR as seen in FIG. 4 is much lesscrystalline (e.g., crystallinity of less than about 10%) than that ofthe native starch blend (crystallinity of about 50%). The difference indiffraction pattern evidences that a substantial chemical change hasoccurred in the material, due to processing from the native starchesinto ESR. For example, while there is a prominent diffraction peakbetween 20-25° with the native starch, no such peak is exhibited in theESR. The native starch further shows a strong peak at about 45° (at anintensity of 0.5 to 0.6), which peak is greatly reduced in the ESR (onlyof about 0.25 to 0.3). Across nearly the entire spectrum, thediffraction intensities are higher for the native starches than for theESR, with the exception of from about 18° to about 22°, as shown. Theelevated diffraction intensity seen across a wide spectrum is indicativeof greater crystallinity of the native starches as compared to the ESR.Numerous other differences also exist, as shown.

By way of example, the carbohydrate-based (e.g., starch-based) polymericmaterial used in making films according to the present disclosure mayhave a crystallinity of less than about 40%, less than about 35%, lessthan about 30%, less than about 25%, less than about 20%, less thanabout 15%, less than about 10%, less than about 8%, less than about 6%,less than about 5%, or less than about 3%. Any suitable test mechanismfor determining crystallinity may be used, e.g., including but notlimited to FTIR analysis, X-ray diffraction methods, and symmetricalreflection and transmission techniques. Various suitable test methodswill be apparent to those of skill in the art.

In addition to the differences in the microstructure of the finished ESRas compared to the starting materials, films, bottles, sheets,disposable utensils, plates, cups, or other articles produced from ablend including the starch-based polymeric material are different fromarticles that are otherwise similar, but formed using conventional TPSand starch powder, or “green” sustainable polymeric materials alone. Forexample, articles formed by blending the starch-based polymericmaterials such as ESR as described herein with a sustainable polymericmaterial do not have “sea-island” features that are common when blendingconventional TPS materials with polymeric materials such aspolyethylene. Properties of the different films can be seen by comparingthe physical properties of films as shown in Table 11 of Example 5below. In particular, Table 11 compares the physical properties of filmsmade by blending starch-based polymeric materials as contemplated hereinwith polyethylene versus a conventional TPS blended with PE (CardiaBL-F). In addition to the differences in properties seen in Table 11,films based on conventional TPS materials such as Cardia BL-F, even ifthey were to incorporate a “green” sustainable polymeric material inplace of the PE are not biodegradable, and not compostable. As describedherein, use of the carbohydrate or starch-based polymeric materials asdescribed herein in forming an article with a sustainable polymericmaterial results in not just the carbohydrate-based or starch-basedmaterial being biodegradable, but at least a portion of the sustainablepolymeric material becoming biodegradable (even where the sustainablepolymeric material alone may not be biodegradable). Such results do notoccur when blending with typical TPS materials. Such differences inbiodegradability clearly illustrate that there are significantstructural differences in the resulting films and other articles, as theentire composite structure (i.e., the film or other structure) may becapable of being biodegraded, as shown by the various examples below.

Without being bound to any particular theory, it is believed that thecarbohydrate-based polymeric resins may reduce the crystallinity of theblended products, interrupting the crystallinity and/or hygoscopicbarrier characteristics of the biopolyethylene or other sustainableplastic material in a way that allows water and bacteria to degrade thearrangements and linkages of otherwise non-biodegradable plasticmolecules of the blend along with the carbohydrate-based polymeric resinmaterial, where the sustainable “green” polymer originally had suchcharacteristics. In other words, the long polymer chains ofbiopolyethylene or other non-biodegradable sustainable plastic materialare more easily broken by chemical and mechanical forces that exist inenvironments that are rich in bacteria and microorganisms, when blendedwith carbohydrate-based polymeric materials as contemplated herein.Subsequently, the microorganisms that exist naturally in a disposalenvironment (e.g., in a landfill) can consume the remaining smallermolecules so that they are converted back into natural components (suchas CO₂, CH₄, and H₂O).

For example, truly biodegradable plastics decompose into naturalelements or compounds such as carbon dioxide, methane, water, inorganiccompounds, or biomass via microbial assimilation (e.g., the enzymaticaction of microorganisms on the plastic molecules). Biodegradation ofplastics can be enabled by first breaking down the polymer chains viaeither chemical or mechanical action but may only be fully accomplishedthrough decomposition of the molecules by microbial assimilation.

Plastics made from petrochemical feedstocks or derived from plantsources begin life as monomers (e.g., single small molecules that canreact chemically with other small molecules). When monomers are joinedtogether, they become polymers (“many parts”), known as plastics. Beforebeing joined together, many monomers are readily biodegradable, althoughafter being linked together through polymerization, the molecules becomeso large and joined in such arrangements and linkages that microbialassimilation by microorganisms is not practical within any reasonabletime frame.

Polymers are formed with both crystalline (regularly packed) structuresand amorphous (randomly arranged) structures. Many polymers contain ahigh degree of crystallinity with some amorphous regions randomlyarranged and entangled throughout the polymeric structure.

ESR materials available from BiologiQ are formed from starting starchmaterials which are highly crystalline, but in which the finished ESRplastic resin material exhibits low crystallinity (substantiallyamorphous). Such starch-based polymer materials are used as a startingmaterial in the production of articles as described herein. ESR is,therefore, plastic that is made from starch. Because of its natural,starch-based origin and carefully controlled linkage types, themolecules (size and links) of plastic made with ESR are highlysusceptible to biodegradation by enzymatic reactions caused from theintroduction of humidity (water) and bacteria or other microorganisms,as evidenced by the experimental test results included herein.

Polyolefins such as rigid forms of polyethylene and polypropylene have ahigh degree of crystallinity and are made by converting monomermolecules (whether petroleum derived or derived from ethanol or othersmall building block molecules derived from plant sources) into longchain polymers. The bonds created when connecting the monomers to formlong polymer chains are strong and difficult to break. Films and otherarticles formed from such polymeric materials (whetherpetrochemical-based or sustainable are often not biodegradable (e.g., atleast in the case of “green” PE, “green” PP, and bioPET). Even if agiven article were formed from a blend of such “green” sustainablepolymeric materials and TPS, it would not normally suddenly acquirebiodegradability characteristics (other than the starch portion of theblend which may sometimes biodegrade).

Applicant has developed a process for making articles from a blend of astarch-based polymeric material having low crystallinity withpolyolefin-based or other polymeric materials, such as polyethylene,that have a relatively high crystallinity. The resulting thermoplasticblend has a higher elastic modulus (stiffness, or strength) thanpolyethylene or other plastic and can be used to make plastic films orother articles that are stronger than the same articles made with purepolyethylene or other pure plastic. For example, Table 11 of Example 5shows physical properties of films produced with a blend of PE and astarch-based polymeric material (such as ESR) as compared to a 100%polyethylene film and as compared to a film formed from a blend of aconventional TPS and polyethylene (i.e., Cardia BL-F). Results fromthird party testing detailed in the Examples provide evidence that filmsaccording to the present invention will exhibit biodegradation of notjust the renewable content (i.e., the ESR), but any petrochemical-basedor the “green” sustainable polymeric material as well. Such results areparticularly surprising, unexpected, and advantageous.

Returning to FIG. 1, at 106, the process 100 includes mixing the one ormore sustainable polymeric materials and the one or morecarbohydrate-based polymeric materials to produce a mixture ofmaterials. In some cases, the mixing of the one or more sustainablepolymeric materials and the one or more carbohydrate-based materials canbe performed using one or more mixing devices. In a particularimplementation, a mechanical mixing device can be used to mix the one ormore sustainable polymeric materials and the one or morecarbohydrate-based polymeric materials. In an implementation, at least aportion of the components of the mixture of the materials can becombined in an apparatus, such as an extruder, an injection moldingmachine, or the like. In other implementations, at least a portion ofthe components of the mixture of the materials can be combined beforebeing fed into the apparatus.

The one or more carbohydrate-based polymeric materials can be present inthe mixture of materials an amount of at least 1%, at least 2%, at least3%, at least 4%, at least 5%, at least 10%, at least 15%, at least 20%,at least 25%, at least 30%, at least 35%, at least 40%, at least 45%, nogreater than 99%, no greater than 95%, no greater than 90%, no greaterthan 80%, no greater than 70%, no greater than 60%, no greater than 50%,from 2% to 98%, from 20% to 40%, from 10% to 40%, from 20% to 30%, from50% to 80%, or from 40% to 60% by weight of the mixture of materials.More than one carbohydrate-based polymeric material may be used, ifdesired.

The “green” sustainable polymeric material can be present in the mixtureof materials in an amount of at least 1%, at least 2%, at least 3%, atleast 4%, at least 5%, at least 10%, at least 15%, at least 20%, atleast 25%, at least 30%, at least 35%, at least 40%, at least 45%, atleast 50%, no greater than 99%, no greater than 95%, no greater than90%, no greater than 85%, no greater than 80%, no greater than 75%, nogreater than 70%, no greater than 65%, or no greater than 60%, from 2%to 98%, from 50% to 90%, from 65% to 75%, from 20% to 50%, or from 40%to 60% by weight of the mixture of materials. More than one sustainablepolymeric material may be used in the mixture, if desired.

A compatibilizer may be present in the mixture of materials. Thecompatibilizer can be mixed with the sustainable polymeric material, thecarbohydrate-based polymeric material, mixed with both, or providedseparately. Often the compatibilizer may be provided with at least oneof the polymeric materials, included in the masterbatch formulation. Thecompatibilizer can be a modified polyolefin, such as a maleic anhydridegrafted polypropylene, a maleic anhydride grafted polyethylene, a maleicanhydride grafted polybutene, or a combination thereof. Thecompatibilizer can also include an acrylate based co-polymer. Forexample, the compatibilizer can include an ethylene methyl acrylateco-polymer, an ethylene butyl-acrylate co-polymer, or an ethylene ethylacrylate co-polymer. Additionally, the compatibilizer can include apoly(vinyacetate) based compatibilizer. In an embodiment, thecompatibilizer may be a grafted version of the sustainable polymericmaterial (e.g., maleic anhydride grafted polyethylene where thesustainable polymeric material is “green” polyethylene).

The mixture of materials may include at least 0.5%, at least 1%, atleast 2%, at least 3%, at least 4%, at least 5%, no greater than 50%, nogreater than 45%, no greater than 40%, no greater than 35%, no greaterthan 30%, no greater than 25%, no greater than 20%, no greater than 15%,no greater than 10%, no greater than 9%, no greater than 8%, no greaterthan 7%, no greater than 6%, from 0.5% by weight to 12%, from 2% to 7%,or from 4% to 6% by weight of a compatibilizer.

Although certainly not required, and in at least some embodiments theinclusion of such would be best avoided, it is within the scope of thepresent invention to include any of a variety of UV and OXO degradableadditives, such as PDQ-M, PDQ-H, BDA, and OxoTerra™ from Willow RidgePlastics, OX1014 from LifeLine, or organic additives such as Restore® byEnso, EcoPure® by Bio-Tec Environmental, ECM Masterbatch Pellets 1M byECM Biofilms, or Biodegradable 201 and/or Biodegradable 302 BioSphere®.Other additives, for example, for increased strength (e.g., Biomax®Strong from Dupont), or otherwise may be included.

One or more additives can be included in the mixture of materials in anamount of at least 0.5%, at least 1%, at least 1.5%, at least 2%, atleast 2.5%, at least 3%, at least 4%, of no greater than 10%, no greaterthan 9%, no greater than 8%, no greater than 7%, no greater than 6%, nogreater than 5%, from 0.2% to 12%, from 1% to 10%, from 0.5% to 4%, orfrom 2% by weight to 6% by weight of the mixture.

Referring to FIG. 1, at 108, the process 100 includes heating themixture of materials. In an implementation, the mixture of materials canbe heated to a temperature of at least 100° C., at least 110° C., atleast 115° C., at least 120° C., at least 125° C., at least 130° C., atleast 135° C., at least 140° C., no greater than 200° C., no greaterthan 190° C., no greater than 180° C., no greater than 175° C., nogreater than 170° C., no greater than 165° C., no greater than 160° C.,no greater than 155° C., no greater than 150° C., from 95° C. to 205°C., from 120° C. to 180° C., or from 125° C. to 165° C.

The mixture of materials including the sustainable polymeric materialand carbohydrate-based polymeric material can be heated in one or morechambers of an extruder. In some cases, one or more chambers of theextruder can be heated at different temperatures. The speed of one ormore screws of the extruder can be any desired rate.

At 110, an article is produced using the mixture of materials. In somecases, the article can include a film. In other cases, the article canbe formed from a film. In other embodiments, the article can have ashape based on a design, such as a mold (e.g., injection molded). Anyconceivable article formed of plastic may be formed from the mixture,e.g., including but not limited to films, bags, bottles, caps, lids,sheets, boxes, plates, cups, utensils, and the like. Where the articleis a film, the film can be formed using a die by injecting a gas intothe heated mixture of material to form the film (i.e., blowing thefilm). Films can be sealed and/or otherwise modified to be in the formof a bag or other article.

Where the article is a film, the film can be comprised of a single layeror multiple layers. The film or any individual layers can have athickness of at least 0.001 mm, at least 0.002 mm, at least 0.004 mm, atleast 0.01 mm, at least 0.02 mm, at least 0.03 mm, at least 0.05 mm, atleast 0.07 mm, at least 0.10 mm, no greater than 1 mm, no greater than0.5 mm, no greater than 0.1 mm, from about 0.05 mm to about 0.5 mm, orfrom 0.02 mm to 0.05 mm.

Films or other articles can have strength characteristics that arecharacterized through testing, such as a dart drop impact test (ASTMD-1709), tensile strength at break test (ASTM D-882), tensile elongationat break test (ASTM D-882), a secant modulus test (ASTM D-882), and/oran Elmendorf Tear test (ASTM D-1922). Films can have a dart drop impacttest value of at least 100 g, 150 g, at least 175 g, at least 200 g, atleast 225 g, at least 250 g, at least 275 g, at least 300 g, no greaterthan 450 g, no greater than 400 g, no greater than 375 g, no greaterthan 350 g, or no greater than 325 g, from 140 g to 425 g, from 200 g to400 g, from 250 g to 350 g, from 265 g to 330 g. In an implementation,such values may be for whatever the thickness of the film is. In anotherimplementation, such values may for a 1 mil thickness film formed fromthe mixture of materials.

The article can have a tensile strength at break test value in themachine direction of at least 3.5 kpsi, at least 3.7 kpsi, at least 3.9kpsi, at least 4.1 kpsi, at least 4.3 kpsi, or at least 4.5 kpsi, nogreater than 5.5 kpsi, no greater than 5.3 kpsi, no greater than 5.1kpsi, no greater than 4.9 kpsi, or no greater than 4.7 kpsi, from 3.5kpsi to 5.5 kpsi, or from 4.1 kpsi to 4.9 kpsi.

The article can have a tensile strength at break test value in thetransverse direction of at least 3.2 kpsi, at least 3.4 kpsi, at least3.6 kpsi, at least 3.8 kpsi, at least 4.0 kpsi, at least 4.2 kpsi, nogreater than 5.7 kpsi, no greater than 5.5 kpsi, no greater than 5.3kpsi, no greater than 5.1 kpsi, no greater than 4.9 kpsi, no greaterthan 4.7 kpsi, no greater than 4.5 kpsi, from 3.2 kpsi to 5.7 kpsi, orfrom 3.6 kpsi to 5.0 kpsi.

The article can have a tensile elongation at break test value in themachine direction of at least 550%, at least 560%, at least 570%, atleast 580%, at least 590%, at least 600%, at least 610%, at least 620%,no greater than 725%, no greater than 710%, no greater than 700%, nogreater than 680%, no greater than 665%, no greater than 650%, nogreater than 635%, from 550% to 750%, or from 600% to 660%.

The article can have a tensile elongation at break test value in thetransverse direction of at least 575%, at least 590%, at least 600%, atleast 615%, at least 630%, or at least 645%, no greater than 770%, nogreater than 755%, no greater than 740%, no greater than 725%, nogreater than 710%, no greater than 695%, no greater than 680%, from 575%to 775%, or from 625% to 700%.

Where applicable the article can have an Elmendorf tear force test valuein the machine direction of at least 280 g/mil, at least 300 g/mil, atleast 320 g/mil, at least 340 g/mil, or at least 360 g/mil, no greaterthan 450 g/mil, no greater than 430 g/mil, no greater than 410 g/mil, nogreater than 390 g/mil, or no greater than 370 g/mil, from 275 g/mil to475 g/mil, or from 325 g/mil to 410 g/mil.

Where applicable the article can have an Elmendorf tear force test valuein the transverse direction of at least 475 g/mil, at least 490 g/mil,at least 500 g/mil, at least 525 g/mil, at least 540 g/mil, or at least550 g/mil, no greater than 700 g/mil, no greater than 680 g/mil, nogreater than 650 g/mil, no greater than 625 g/mil, no greater than 600g/mil, no greater than 580 g/mil, or no greater than 570 g/mil, from 475g/mil to 725 g/mil, or from 490 g/mil to 640 g/mil.

Where applicable the article can have a secant modulus of elasticitytest value in the machine direction of at least 20 kpsi, at least 22kpsi, at least 24 kpsi, at least 26 kpsi, at least 28 kpsi, or at least30 kpsi, no greater than 40 kpsi, no greater than 38 kpsi, no greaterthan 36 kpsi, no greater than 34 kpsi, or no greater than 32 kpsi, from20 kpsi to 40 kpsi, or from 25 kpsi to 35 kpsi.

Where applicable the article can have a secant modulus of elasticitytest value in the transverse direction of at least 20 kpsi, at least 22kpsi, at least 24 kpsi, at least 26 kpsi, at least 28 kpsi, or at least30 kpsi, no greater than 40 kpsi, no greater than 38 kpsi, no greaterthan 36 kpsi, no greater than 34 kpsi, or no greater than 32 kpsi, from20 kpsi to 40 kpsi, or from 25 kpsi to 35 kpsi.

In some cases, articles including a carbohydrate-based polymericmaterial formed from a mixture of two or more starches have values ofstrength properties that are greater than articles including acarbohydrate-based polymeric material formed from a single starch. Forexample, an article including a carbohydrate-based polymeric materialformed from a mixture of two or more starches can have a dart dropimpact test value (in grams or g/mil of thickness) that is at leastabout 10% greater than an article where the carbohydrate-based polymericmaterial is formed from a single starch, at least about 25% greater, atleast about 50% greater, at least about 75% greater, from 10% greater to150% greater or from 60% greater to 120% greater than the same articlebut including a carbohydrate-based polymeric material formed from asingle starch.

In other words, where the starch-based polymeric material that goes intothe article is formed from two or more different types of starches theresulting strength is greater than if either starch were used alone tomake the starch-based polymeric material. There is thus a synergisticstrengthening effect that is achieved when using two or more differentstarches to make the starch-based polymeric material that is included inthe article.

Furthermore, it is not necessary that a mixture of starches be used informing the carbohydrate-based polymeric material to achieve increasedstrength results. For example, two different carbohydrate-basedpolymeric materials (one formed from one starch (e.g., corn), and theother formed from another starch (e.g., potato) could similarly beblended with a polyolefin or other plastic to form a film or otherdesired article that would exhibit increased strength as compared tosuch an article that was formed from only one or the other of thestarches.

When subjected to biodegradation testing (e.g., whether biomethanepotential testing, or any applicable ASTM standard, such as ASTM D-5511,ASTM D-5526, ASTM D-5338, or ASTM D-6691. Under such testing, and withina given time period (e.g., 30 days, 60 days, 90 days, 180 days, 365 days(1 year), 2 years, 3 years, 4 years, or 5 years, the article may showsubstantial biodegradation of the total polymeric content, and/or thesustainable polymeric content (apart from the starch-based polymericcontent). Biomethane potential testing is typically conducted over 30 or60 days, although sometimes for as long as 90 days. The longer timeperiod tests are more typically applicable under any of the abovementioned ASTM standards. For example, an article that may be free orsubstantially free of a biodegradation enhancing additive may showbiodegradation that is greater than the starch-based polymeric materialcontent thereof, indicating that the other polymeric material(s) arealso biodegrading (or exhibit the potential to biodegrade under abiomethane potential test).

Particularly when subjecting the articles to testing simulatingbiodegradation under landfill or other degradation conditions (e.g.,composting conditions, or marine conditions) for 180 days, 200 days, 365days (1 year), 2 years, 3 years, or 5 years, the biodegradation can begreater than the weight percent of carbohydrate-based polymericmaterials within the article. In other words, inclusion of the describedcarbohydrate-based polymeric materials can result in at least somebiodegradation of the sustainable polymeric material (which materialsalone are not biodegradable, at least in the case of “green” PE, “green”PP, and bioPET). For example, an article that is formed from a blend ofthe carbohydrate-based polymeric materials and “green” PE may exhibitbiodegradation after such periods of time that is greater than theweight fraction of the carbohydrate-based polymeric materials in thefilm, indicating that the “green” PE (heretofore considered to not bebiodegradable) is actually being biodegraded, with thecarbohydrate-based polymeric material. Such results are surprising, andparticularly advantageous. For example, such an article not onlyexhibits increased environmental sustainability (as potentially theentirety of the polymeric content of the article is derived fromsustainable plant materials in the form of starch for thecarbohydrate-based polymeric material and ethanol (or another smallmolecule building block) in the case of the sustainable polymericmaterial), but it now also exhibits biodegradability characteristics,where the comparable bag or other film formed from 100% “green” PE (oreven a blend of conventional TPS and “green” PE) did not have suchcharacteristics. Furthermore, as described above, the strength of thearticle can be greater than that of the 100% “green” PE article. Evencost can potentially be comparable. Such a collection of characteristicsmarks a significant advancement in the art.

Biomethane potential testing determines the potential for anaerobicbiodegradation based on methanogenesis as a percent of totalmethanogenesis potential. Biomethane potential testing can be used topredict biodegradability of the tested samples according to the ASTMD-5511 standard and the biomethane potential testing can be conductedusing one or more conditions from the ASTM D-5511 standard. For example,the biomethane potential testing can take place at a temperature ofabout 52° C. Additionally, the biomethane potential testing can havesome conditions that are different from those of ASTM D-5511, e.g., toaccelerate the test to be completed within the typical 30, 60, orsometimes as long as 90 days. Biomethane potential testing can employ aninoculum having from 50% to 60% by weight water and from 40% to 50% byweight organic solids. For example, an inoculum used in biomethanepotential testing can have 55% by weight water and 45% by weight organicsolids. Biomethane potential testing can also take place at othertemperatures, such as from 35° C. to 55° C. or from 40° C. to 50° C.

When subjected to biodegradation testing, an article having no greaterthan about 2% by weight of a biodegradation enhancing additive (or beingfree thereof) and having an amount of carbohydrate-based polymericmaterial and sustainable polymeric material as described herein canexhibit enhanced degradation, as a result of the introduction of thecarbohydrate-based polymeric material into the article. For example, atleast 5%, at least 10%, at least 15%, at least 20%, at least 25%, atleast 30%, at least 35%, at least 40%, at least 45%, at least 50%, atleast 55%, at least 60%, at least 65%, at least 70%, at least 75%, atleast 80%, at least 85%, at least 90%, or even at least 95% of thenon-carbohydrate-based polymeric material (e.g., the “green” sustainablepolymeric material) may biodegrade over a period of at least about 1year, at least about 2 years, at least about 3 years, or at least about5 years when subjected to landfill, composting, and/or marine conditions(or conditions simulating such). Such biodegradation is particularlyremarkable and advantageous. Thus not only does the carbohydrate-basedpolymeric material biodegrade, but the “green” sustainable polymericmaterial does as well.

The Examples show that with increased time, the amount of biodegradationcan be very high, such that in at least some implementations,substantially the entire article biodegrades (e.g., biodegradation of atleast about 85%, at least about 90%, or at least about 95% within 180days, or 200 days, or 365 days (1 year), within 2 years, within 3 years,within 5 years, or other period).

FIG. 2 illustrates components of an example manufacturing system 200 toproduce articles according to the present disclosure. In some cases, themanufacturing system 200 can be used in the process 100 of FIG. 1. In anillustrative example, the manufacturing system 200 is an extruder, suchas a single screw extruder or a twin screw extruder.

In an implementation, one or more sustainable polymeric materials andone or more carbohydrate-based polymeric materials are provided via afirst hopper 202 and a second hopper 204. The one or more sustainablepolymeric materials can include one or more “green” sustainablepolyolefin-based polymeric materials. For example, the one or moresustainable polymeric materials can include a “green” polyethylene.Additionally, the one or more carbohydrate-based polymeric materials caninclude one or more starch-based polymeric materials. A compatibilizermay be included with either or both polymeric materials (e.g., in amasterbatch thereof).

The one or more carbohydrate-based polymeric materials and the one ormore sustainable polymeric materials can be mixed in a first chamber 206to produce a mixture of materials. In some cases, the mixture ofmaterials can include from 10% by weight to 40% by weight of the one ormore carbohydrate-based polymeric materials, from 60% by weight to 89%by weight of the one or more sustainable polymeric materials, and from1% by weight to 9% by weight of the one or more compatibilizers. Theranges of course may be varied outside the above ranges, depending ondesired characteristics.

In the example implementation shown in FIG. 2, the mixture of materialscan pass through a number of chambers, such as the first chamber 206, asecond chamber 208, a third chamber 210, a fourth chamber 212, a fifthchamber 214, and an optional sixth chamber 216. The mixture of materialscan be heated in the chambers 206, 208, 210, 212, 214, 216. In somecases, a temperature of one of the chambers can be different from atemperature of another one of the chambers. In an illustrative example,the first chamber 206 is heated to a temperature from 120° C. to 140°C.; the second chamber 208 is heated to a temperature from 130° C. to160° C.; the third chamber 210 is heated to a temperature from 135° C.to 165° C.; the fourth chamber 212 is heated to a temperature from 140°C. to 170° C.; the fifth chamber 214 is heated to a temperature from145° C. to 180° C.; and the optional sixth chamber 216 is heated to atemperature from 145° C. to 180° C.

The heated mixture can then be extruded using a die 218 to form anextruded object, such as a film, sheet, or the like. Injection molding,thermoforming, or other plastic production processes may be used tomanufacture various articles such as utensils, plates, cups bottles,caps or lids therefore, or the like. In film blowing, a gas can beinjected into the extruded object to expand it with a pressure from 105bar to 140 bar. The resulting tube 220 can be drawn up through rollers222 to create a film 224 with a thickness typically from 0.02 mm (about0.8 mil) to 0.05 mm (about 2 mil). Even thinner films can be made usingthe blends as described herein, e.g., having a thickness as little as0.1 mil (0.004 mm). Of course, thicknesses greater than 2 mil can alsobe achieved. In some cases, the film 224 can be comprised of a singlelayer. In other cases, the film 224 can be comprised of multiple layers.For example, the film 224 can be comprised of multiple layers. Wheremultiple layers are present, at least one of the layers may include thecarbohydrate-based polymeric material. In some embodiments, thecarbohydrate-based polymeric material may be present in one or moreouter layers. In another embodiment, the carbohydrate-based polymericmaterial may be present in an inner layer. Where no carbohydrate-basedpolymeric material is included in the outer layer(s), biodegradation ofthe outer layer(s) may not occur.

The concepts described herein will be further described in the followingexamples, which do not limit the scope encompassed by the claims.

EXAMPLES Example 1

A starch-based polymer was formed from 27% tallow glycerin (99% pureglycerin), and 73% starch, exclusive of the water used. Thefinished-starch-based polymer included <1% water. The starch-basedpolymer was mixed with LLDPE and anhydride-modified LLDPE in proportionsof 25%, 70%, and 5%, respectively, by weight. Eleven samples wereprepared and blown into films. The temperature settings of the extruderused are shown in Table 3. B1, B2, B3, B4, and B5 refer to temperaturesettings at different locations of the barrel of the extruder and AD1,D1, and D2 refer to the temperature settings at different locations inthe die section of the extruder.

TABLE 3 Extruder Temp. B1 B2 B3 B4 B5 AD1 D1 D2 Set 130 140 145 150 160160 160 160 Value

The extruder blow settings are shown in Table 4.

TABLE 4 Extruder Melt Temper- Extruder Take-Up ature Pres- Motor SpeedSetting sure Screw Setting Blower (meters/ Blow (° C.) (bar) RMP (Amps)Speed min) Set 148 132 17 32.0 0 7.0 Value (Samples 1-11) Set 147 115 1732.0 0 7.0 Value (Sample 12)

70% of each film was LLDPE, 25% was the starch-based polymer, and 5% ofeach film was anhydride-modified LLDPE. The films then were tested usinga falling dart impact test according to ASTM D-1709. The strength testresults of these tests are shown in Table 5. Dart strength per mil ofthickness can simply be calculated by dividing the measured dart impactstrength (e.g., from ASTM D-1709) by the thickness of the tested film.This example could be performed with a “green” PE, and similar resultsshowing increased strength would be achieved. Example 16 hereafter showsstrength data where a film was actually blown from biopolyethylene, acompatibilizer, and the starch-based polymer.

TABLE 5 Sample No. Film Thickness (Mil) Dart Test (g) 1 1.535 >387 21.50 >387 3 1.50 >387 4 1.50 347 5 1.45 347 6 1.55 387 7 1.55 387 81.50 >387 9 1.55 387 10 1.55 >387 11 1.50 >387 12 2.00 227

Example 2

A starch-based polymer was formed from 27% tallow glycerin (99% pureglycerin) and 73% starch, exclusive of the water used. The finishedstarch-based polymer included <1% water. The starch-based polymer wasmixed with LLDPE and anhydride-modified LLDPE in proportions of 25%,70%, and 5%, respectively, by weight. Two samples were prepared andblown into films. The temperature settings of the extruder used areshown in Table 6.

TABLE 6 Extruder Temp. B1 B2 B3 B4 B5 B6 AD1 D1 D2 Set 130 150 155 160165 165 165 170 170 Value

The extruder blow settings are shown in Table 7.

TABLE 7 Extruder Melt Temper- Extruder Take-Up ature Pres- Motor SpeedSetting sure Screw Setting Blower (meters/ (° C.) (bar) RPM (Amps) Speedminute) Set 149 121 16.0 35.0 0 6.0 Value

70% of each film was LLDPE, 25% was the starch-based polymer, and 5% ofeach film was anhydride-modified LLDPE. The films then were tested usinga falling dart impact test according to ASTM D-1709. The strength testresults (in grams) of these tests are shown in Table 8. This examplecould be performed with a “green” PE, and similar results showingincreased strength would be achieved. Example 16 hereafter showsstrength data where a film was actually blown from biopolyethylene, acompatibilizer, and the starch-based polymer.

TABLE 8 Sample No. Film Thickness (Mil) Dart Test (g) 1 1.575 347 21.335 362

Example 3

In order to test the strength characteristics resulting from variouscombinations of starch, 17 starch-based polymers were formed usingwater, tallow glycerin (99% pure glycerin) and starch. Exclusive of thewater, the fraction of the starch-based polymer formed from glycerinvaried from 27% to 32%, while the fraction formed from the starch variedfrom 68% to 73%. All finished starch-based polymers exhibited <about 1%water, and were mixed with LLDPE and anhydride-modified LLDPE inproportions of 25%, 70%, and 5%, respectively, by weight. The resultingmixtures were then extruded and blown into films. The films were thentested using a falling dart drop impact test according to ASTM D-1709.The combinations of starches tested and strength test results are shownin Table 9A. The two thickness values for each sample in Table 9Acorrespond to the minimum and maximum measured thickness for each sample(as there was some variation within each film). As can be seen from theresults shown in Table 9A-9B, samples formed from a mixture of starcheshave a dart drop impact test value (in grams) that is greater than thedart drop impact test value of samples formed from a single starch.Table 9B shows the calculated percentages in increased strength ascompared to what might be expected (e.g., a weighted strength based onpercentage of each starch in the mixture). The increases in strength areremarkable, and unexpected. This example could be performed with a“green” PE, and similar results of increased strength would be achieved.

TABLE 9A Water Content (Starch- Dart Sample based Starch Content (%)Thickness Test No. Polymers) Potato Corn Tapioca (mm) (g) 1 0.58 0 100 00.040 0.045 137 2 0.73 100 0 0 0.040 0.045 167 3 0.80 0 100 0 0.0400.045 167 4 0.93 100 0 0 0.030 0.035 167 5 0.49 0 0 100 0.035 0.040 1976 0.55 0 0 100 0.030 0.035 212 7 1.03 33.33 33.33 33.33 0.030 0.035 2428 1.04 20 20 60 0.030 0.035 267 9 0.97 60 20 20 0.025 0.030 252 10 0.930 0 100 0.025 0.030 257 11 0.94 20 0 80 0.025 0.030 257 12 1.37 20 80 00.025 0.030 257 13 0.95 80 0 20 0.030 0.035 302 14 1.19 20 60 20 0.0300.035 322 15 0.96 0 80 20 0.025 0.030 277 16 1.05 80 20 0 0.025 0.030317 17 0.81 0 20 80 0.025 0.030 322

TABLE 9B Mean Film Dart Percent ESR Thickness Strength Increase in DartSample No. Used (mil) (g/mil) Strength (%) 1 GS-270 1.673 81.9 N/A 2GS-270 1.673 99.8 N/A 3 GS-300 1.673 99.8 N/A 4 GS-300 1.280 130.5 N/A 5GS-270 1.476 133.4 N/A 6 GS-300 1.280 165.7 N/A 7 GS-300 1.280 189.143.3% 8 GS-300 1.280 208.7 43.4% 9 GS-300 1.083 232.8 77.1% 10 GS-3301.083 237.4 N/A 11 GS-300 1.083 237.4 49.6% 12 GS-300 1.083 237.4 124.0%13 GS-300 1.280 236.0 71.6% 14 GS-300 1.280 251.7 111.3% 15 GS-300 1.083255.8 126.4% 16 GS-300 1.083 292.8 135.4% 17 GS-300 1.083 297.4 95.0%

Example 4

Using the same protocols as described in Example 3, 11 additionalcombinations of starches were tested. Specifically, 11 starch-basedpolymers were formed from 27% tallow glycerin (99% pure glycerin) and73% starch, exclusive of the water. Each finished starch-based polymerexhibited <about 1% water, and was mixed with LLDPE andanhydride-modified LLDPE in proportions of 25%, 70%, and 5%,respectively, by weight. The resulting mixtures were then extruded andblown into films. 70% of each film was LLDPE, 25% was the starch-basedpolymer, and 5% of each film was anhydride-modified LLDPE. The filmswere then tested using a falling dart impact test according to ASTMD-1709. The combinations of starches tested and strength test results(in grams) are shown in Table 10. As with the results shown in Tables9A-9B, the results of Table 10 show that samples formed from a mixtureof starches have dart drop impact test values that are greater than thedart drop impact test values of samples formed from a single starch.Such an increase in strength achieved by using a mixture of differentstarches in forming the starch-based polymeric material, from which thefilm is formed (with the LLDPE) is surprising an unexpected.

TABLE 10 Percent Increase Thick- Dart Dart in Dart Sample Starch Content(%) ness Test Strength Strength No. Potato Corn Tapioca (mil) (g)(g/mil) (%) 1 0 100 0 1.535 347 226.1 N/A 2 100 0 0 1.535 362 235.8 N/A3 0 0 100 1.550 367 236.8 N/A 4 80 20 0 1.550 387 249.7 6.8% 5 0 20 801.550 387 249.7 6.4% 6 0 80 20 1.550 387 249.7 9.4% 7 0 10 90 1.550 387249.7 5.9% 8 33.33 33.33 33.33 1.500 387 258 10.9% 9 80 0 20 1.500 387258 9.3% 10 10 0 90 1.500 387 258 9.0% 11 0 90 10 1.500 387 258 13.6%

Although the strength increase values seen in Table 10 differ from thoseof Example 3 (in Tables 9A-9B), both show a synergistic strengthincrease, beyond what would be expected, when different starches areused in forming the ESR. Various specific process conditions, such astemperature, blow up ratio, and the like may affect actual increasesachieved.

FIG. 5 charts dart impact test strength for different thickness films(0.5 mil, 1 mil, 1.5 mil, 2.0 mils) based on percentage of starch-based“ESR” in the film. The ESR used in the films formed shown in FIG. 5 wasformed from a blend of starches including 90% corn starch and 10% potatostarch. FIG. 5 shows how the strength of the film increases withincreasing ESR percentage, up to a maximum strength at about 20% toabout 25% ESR. The balance of the blend included polyethylene and anappropriate compatibilizer, as described herein.

FIG. 6 charts dart impact test strength for different thickness films(from about 0.1 mil up to 2 mils) for films including 25%carbohydrate-based polymeric material, with the balance being a smallfraction of compatibilizer (e.g., about 5%) as described herein, and PE(about 70%). Although the actual plotted data are for syntheticpetro-chemical based PE, values for biopolyethyelene are expected to besimilar. FIG. 6 also shows comparative strength for 100% PE films (whichwould be similar for 100% green PE), which are at all points lower thanfor the blend according to the present disclosure. FIG. 6 further showsvarious other tested reference points for produce bags (e.g., bagsprovided to consumers in a supermarket produce section for holdingproduce), for various “haul out” bags (e.g., grocery and other plasticbags provided for carry out), and for potato bags (plastic bags used tohold typically 5, 10 or 20 pounds of potatoes in the produce section ofa supermarket). While the actual measurements shown in FIG. 6 were takenusing LLDPE, it is expected that the values will be similar when using“green” PE. Such expectation that “green” PE will perform similarly toother forms of PE is supported by Example 16, in which films were blownfrom “green” PE and blends of such with ESR.

FIG. 7 charts dart impact test strength for different thickness films(from less than 0.5 mil up to about 2 mils) for various blended filmsaccording to the present disclosure, as well as comparative films (e.g.,100% LLDPE, 100% recycled LLDPE (rLLDPE). In addition to showingstrength characteristics for a film formed from virgin materials (25%ESR, 70% LLDPE, 5% compatibilizer (labeled 25% ESR/75% LLDPE), FIG. 7also shows strength resulting when such a recycled material (rLDESR) isthen blended with virgin materials (labeled 25% ESR/25% rLDESR/50%LLDPE), or where recycled LLDPE (rLLDPE) is used in the blend (labeled25% ESR/25% rLLDPE/50% LLDPE). The strength results are improved ascompared to use of PE polymeric materials, as shown, in addition to thepreviously described characteristics of increased renewability andbiodegradability. While the actual measurements shown in FIG. 7 weretaken using LLDPE formed from non-sustainable sources, it is expectedthat the values will be similar when using “green” PE.

Example 5

A starch-based polymer formed from water, tallow glycerin (99% pureglycerin) and starch, and exhibiting <about 1% water after manufacturewas mixed with LLDPE and anhydride-modified LLDPE in proportions of 25%,70%, and 5%, respectively, by weight. The starch used in forming thestarch-based polymer was a blend of 90% corn starch and 10% potatostarch, by weight. The mixture of the starch-based polymer and the LLDPEwas extruded and blown into a film. 70% was LLDPE, 25% of the film wasthe starch-based polymer, and 5% was anhydride-modified LLDPE. Forcomparison purposes, a second film containing 100% LLDPE was alsoprepared. Using a variety of testing methods a number of strengthcharacteristics were tested, the results of which are shown in Table 9.In Table 11, transverse directions is abbreviated (TD) and machinedirections is abbreviated (MD). The results shown in Table 11 indicatethat the sample formed from the starch-based polymer blend has valuesfor some of the strength tests that are greater than correspondingvalues for the LLDPE sample. This example could be performed with a“green” PE, and similar results would be achieved.

TABLE 11 Sample Test Cardia Form Method CP14102701 LLDPE BL-F FilmThickness Film 1.35 1.35 1.2 (mil) Mass Density Film or ASTM D-792 1.040.92 (SG): Pellets Secant Modulus Film ASTM D-882 30 +/− 1 37.7 +/− 2.2MD, kpsi Secant Modulus Film ASTM D-882   30 +/− 1.3 32.1 +/− 2.4 TD,kpsi Tensile Strength Film ASTM D-882  4.5 +/− 0.4  4.4 +/− 0.2 2.9 MDBreak, kpsi Tensil Strength Film ASTM D-882  4.3 +/− 0.7  4.7 +/− 1.1 TDBreak, kpsi Tensil Elongation Film ASTM D-882 632 +/− 27 571 +/− 25330    MD Break, % Tensile Elongation Film ASTM D-882 664 +/− 32 651 +/−65 TD Break, % Elmendorf Film ASTM D-1922 367 +/− 38 254 +/− 41 Tear MD,g/mil Elmendorf Film ASTM D-1922 568 +/− 70 481 +/− 41 Tear TD, g/milDart Drop Film ASTM D-1709 320 +/− 10 175 +/− 10 200    Impact, gBarrier: OPV Film cc-25, mic/m² 2,916 +/− 49   4,346 +/− 130  23° C, 0%RH day-atm O₂ Barrier: MVPV Film gm/m²-day 24 +/− 3 14 +/− 0 39° C, 100%RH Optical Film ASTM D-1746  7 +/− 1 44 +/− 1 Transparency % Heat SealFilm 40 psi, 0.5 sec 1,400 g/in 1,497 g/in Strength Heat Seal Film130-180° C. 130-180° C. Temperature Range Melt Flow Rate Pellets ASTMD-1238 0.47 g/10 min 1.0 g/10 min Bio Content Film or   25% 0%   33%Pellets Water Content Pellets ASTMD-6980 0.35% 0% 0.60%

Example 6

Seven samples were tested for 32 days to determine biodegradabilitycharacteristics using biomethane potential testing, to determine thepotential for anaerobic biodegradation based on methanogenesis as apercent of total methanogenesis potential. The biomethane potential testwas intended to replicate the conditions of a full-scale anaerobicdigester (landfill). The biomethane potential test was conducted at atemperature of about 52° C. using an inoculum having about 55% by weightwater and about 45% by weight organic solids. The positive controlsample was cellulose and the negative control sample was untreatedpolyethylene. The results of four samples (referred to as 957, 958, 959,and 960) are shown in FIGS. 8A and 8B and in Table 12.

TABLE 12 Inoculum Negative Positive 957 958 959 960 Cumulative Gas 729.6962.5 8184.2 13366.8 2805.7 2995.4 5599.0 Volume (mL) Percent CH₄ (%)18.4 19.3 35.4 29.2 21.8 0.0 33.6 Volume CH₄ (mL) 134.2 185.5 2898.23904.4 612.4 0.0 1880.7 Mass CH₄ (g) 0.10 0.13 2.07 2.79 0.44 0.00 1.34Percent CO₂ (%) 49.9 44.0 44.5 43.4 43.2 40.2 45.4 Volume CO₂ (mL) 364.0423.3 3639.8 5799.9 1211.8 1204.2 2544.1 Mass CO₂ (g) 0.72 0.83 7.1511.39 2.38 2.37 5.00 Sample Mass (g) 1,000 10 10 20.0 20.0 20 20Theoretical 0.0 8.6 4.2 17.1 17.1 17.1 17.1 Sample Mass (g) Biodegraded0.27 0.33 3.50 5.20 0.98 0.65 2.37 Mass (g) Percent 0.7 76.7 28.8 4.12.2 12.3 Biodegraded (%) Adjusted Percent 0.9 100.0 37.5 5.4 2.9 16.0Biodegraded (%)

The results of biomethane potential testing for samples 961, 962, and963 are shown in FIGS. 9A and 9B, and Table 13.

TABLE 13 Inoc- Neg- Pos- ulum ative itive 961 962 963 Cumulative 729.6962.5 8184.2 4286.4 5538.9 5796.5 Gas Volume (mL) Percent 18.4 19.3 35.427.1 31.8 0.0 CH₄ (%) Volume 134.2 185.5 2898.2 1161.9 1759.5 0.0 CH₄(mL) Mass CH₄ 0.10 0.13 2.07 0.83 1.26 0.00 (g) Percent 49.9 44.0 44.542.5 42.7 40.9 CO₂ (%) Volume 364.0 423.3 3639.8 1821.0 2363.9 2370.7CO₂ (mL) Mass 0.72 0.83 7.15 3.58 4.64 4.66 CO₂ (g) Sample Mass 1,000 1010 20.0 20.0 20 (g) Theoretical 0.0 8.6 4.2 17.1 17.1 17.1 Sample Mass(g) Biodegraded 0.27 0.33 3.50 1.60 2.21 1.27 Mass (g) Percent 0.7 76.77.8 11.3 5.9 Biodegraded (%) Adjusted 0.9 100.0 10.1 14.8 7.6 PercentBiodegraded (%)

The content and form of the samples tested can be found in Table 14. Thestarch-based polymer material was formed from 27% glycerin (99% pure)and 73% starch (exclusive of the water), and exhibited <about 1% waterafter manufacture. “Ecoflex” refers to the Ecoflex® plastic productavailable from BASF. Bio-B refers to a degradation enhancing additiveavailable from BiologiQ. This example could be performed with a “green”PE, and similar results would be achieved.

TABLE 14 Maleic Starch- Poly- Anhydride Biode- Sam- Based ethyl-Modified Addi- gradation - ple Polymer ene Ecoflex LLDPE tive EnhancingNo. (%) (%) (%) (%) (%) Additive Form 957 100 0 0 0 — Press- outs 958 2570 5 0 — Film 959 30 65 5 0 — Film 960 25 70 5 0 — Bag 961 25 69 5 1Enso Film Restore 962 25 69.5 5 0.5 Bio-B Film 963 30 15 50 5 0 — Film

Example 7

Seven samples were tested for 91 days to determine biodegradabilitycharacteristics using biomethane potential testing conducted at atemperature of about 52° C. using an inoculum having about 55% by weightwater and about 45% by weight organic solids, to determine the potentialfor anaerobic biodegradation based on methanogenesis as a percent oftotal methanogenesis potential. The positive control sample wascellulose and the negative control sample was untreated polyethylene.The results of sample numbers 957, 958, 959, and 960 (compositions shownin Table 14) are shown in FIGS. 10A and 10B and in Table 15.

TABLE 15 Inoculum Negative Positive 957 958 959 960 Cumulative Gas 811.31067.4 8211.9 18074.3 4045.8 5643.8 10915.8 Volume (mL) Percent CH₄ (%)22.3 23.2 35.5 34.7 32.7 39.4 42.2 Volume CH₄ (mL) 180.6 248.1 2914.56273.2 1321.2 2224.8 4608.8 Mass CH₄ (g) 0.13 0.18 2.08 4.48 0.94 1.593.29 Percent CO₂ (%) 48.4 43.1 44.4 42.6 42.1 39.7 40.3 Volume CO₂ (mL)392.4 460.3 3649.4 7692.5 1703.2 2238.1 4401.5 Mass CO₂ (g) 0.77 0.907.17 15.11 3.35 4.40 8.65 Sample Mass (g) 1,000 10 10 20.0 20.0 20 20Theoretical 1.0 8.6 4.2 17.1 17.1 17.1 17.1 Sample Mass (g) Biodegraded0.31 0.38 3.52 7.48 1.62 2.39 4.83 Mass (g) Percent 0.8 76.1 41.9 7.712.2 26.4 Biodegraded (%) Adjusted Percent 1.1 100.0 55.0 10.1 16.0 34.7Biodegraded (%)

The biomethane potential testing results of sample numbers 961, 962, and963 (compositions shown in Table 14) are shown in FIGS. 11A and 11B andin Table 16. This example could be performed with a “green” PE or other“green” polymeric material, and similar results would be achieved.

TABLE 16 Inoculum Negative Positive 961 962 963 Cumulative Gas 811.31067.4 8211.9 7385.2 13059.8 11733.3 Volume (mL) Percent CH₄ (%) 22.323.2 35.5 38.6 46.3 45.2 Volume CH₄ (mL) 180.6 248.1 2914.5 2849.96052.3 5302.2 Mass CH₄ (g) 0.13 0.18 2.08 2.04 4.32 3.79 Percent CO₂ (%)48.4 43.1 44.4 40.9 39.8 39.6 Volume CO₂ (mL) 392.4 460.3 3649.4 3023.85197.1 4643.4 Mass CO₂ (g) 0.77 0.90 7.17 5.94 10.21 9.12 Sample Mass(g) 1,000 10 10 20.0 20.0 20 Theoretical 0.0 8.6 4.2 17.1 17.1 17.1Sample Mass (g) Biodegraded 0.31 0.38 3.52 3.15 6.03 5.33 Mass (g)Percent 0.8 76.1 16.6 33.4 29.3 Biodegraded (%) Adjusted Percent 1.1100.0 21.8 43.9 38.5 Biodegraded (%)

Example 8

A film was tested for 71 days to determine biodegradabilitycharacteristics using biomethane potential testing conducted at atemperature of about 52° C. using an inoculum having about 55% by weightwater and about 45% by weight organic solids, to determine the potentialfor anaerobic biodegradation based on methanogenesis as a percent oftotal methanogenesis potential. The positive control sample wascellulose and the negative control sample was untreated polyethylene.The film contained 25% starch-based polymer material (with 27% of thestarch-based polymer material being formed from glycerin (99% pure) and73% of the starch-based polymer material being formed from starch,exclusive of the water), and exhibited <about 1% water aftermanufacture). In addition to the 25% by weight starch-based polymer, thefilm also included 1% Biosphere® additive; 5% maleic anhydridecompatibilizer; and 69% modified LLDPE. The results of the biomethanepotential testing of sample number 983 are shown in FIGS. 12A and 12Band in Table 17. This example could be performed with a “green” PE andsimilar results would be achieved.

TABLE 17 Inoc- Neg- Pos- ulum ative itive 983 Cumulative Gas Volume (mL)1021.1 1326.5 8225.8 10104.5 Percent CH₄ (%) 26.3 27.4 35.5 41.7 VolumeCH₄ (mL) 268.4 363.3 2922.7 4214.4 Mass CH₄ (g) 0.19 0.26 2.09 3.01Percent CO₂ (%) 47.6 42.3 44.4 41.9 Volume CO₂ (mL) 185.7 561.2 3654.24230.1 Mass CO₂ (g) 0.95 1.10 7.18 8.31 Sample Mass (g) 1,000 10 10 20.0Theoretical Sample Mass (g) 0.0 8.6 4.2 17.1 Biodegraded Mass (g) 0.400.50 3.52 4.52 Percent Biodegraded (%) 1.1 73.9 24.0 * Adjusted Percent1.4 100.0 32.5 Biodegraded (%)

Example 9

Eight samples (sample numbers 957-963 and 983; compositions shown inExamples 5 and 7) were tested for 91 days to determine biodegradabilitycharacteristics using biomethane potential testing conducted at atemperature of about 52° C. using an inoculum having about 55% by weightwater and about 45% by weight organic solids, to determine the potentialfor anaerobic biodegradation based on methanogenesis as a percent oftotal methanogenesis potential. The positive control sample wascellulose and the negative control sample was untreated polyethylene.The results are shown in Table 18. The results shown in Table 18indicate that samples formed from a mixture of a starch-based polymerand a polyolefin based polymer biodegrades an amount that is greaterthan the amount of the starch-based polymer. In some cases, the samplethat biodegraded more than an amount of the starch-based polymer presentwas free of a biodegradation enhancing additive. Such results aresurprising, and particularly advantageous. This example could beperformed with a “green” PE or other “green” polymeric material, andsimilar results would be achieved.

TABLE 18 % Degraded Item # 32 Days 42 Days 62 Days 71 Days 91 Days 95737.50% 48.40% 55.00% 958 5.40% 8.10% 10.10% 959 2.90% 11.30% 16.00% 96016.00% 30.00% 34.70% 961 10.10% 19.40% 21.80% 962 14.80% 26.40% 43.90%963 7.60% 28.10% 38.50% 983 19.20% 32.50%

Example 10

Four samples (sample numbers 100, 200, 300, and 400) were tested forcompostability using the ASTM D-6400 standard at the time of filing ofthis patent application. The ASTM D-6400 standard specifies aphytotoxicity testing procedure, indicates that the biodegradation ofarticles is to be measured according to the ASTM D-5338-11 test, andthat an elemental analysis is to utilize Table 3 of 40 C.P.R. Part503.13. The compositions of the samples and the biodegradation portionof the compostability test results are shown in Table 19. Thestarch-based polymeric material was formed from a blend of starchesincluding 90% corn starch and 10% potato starch. The first polymericmaterial was a linear low-density polyethylene produced using ametallocene catalyst. A “green” PE material could have been used, andwould provide similar results. The compatibilizer for samples 100 and200 was a Bynel® compatibilizer from DuPont® and the compatibilizer forsamples 300 and 400 was an Amplify compatibilizer from Dow®. Thebiodegradation enhancing additive for samples 100 and 200 was fromBiosphere® and the biodegradation enhancing additive for sample 300 wasfrom ENSO. The second polymeric material was Ecoflex® from BASF, whichis a fossil raw materials-based plastic that is compostable according tothe ASTM D-6400 standard. The 98 day biodegradability results indicatedthe test chamber carbon dioxide measurement as a percentage of atheoretical maximum amount of carbon dioxide for the sample after 98days. The 180 day biodegradability results indicated the test chambercarbon dioxide measurement as a percentage of a theoretical maximumamount of carbon dioxide after 180 days.

FIG. 13A shows the results of the biodegradation portion of the ASTMD-6400 test performed according to ASTM D-5338 for sample 100. FIG. 13Bshows the results of the biodegradation portion of the ASTM D-6400 testperformed according to ASTM D-5338 for sample 200. FIG. 14A shows theresults of the biodegradation portion of the ASTM D-6400 test performedaccording to ASTM D-5338 for sample 300 and FIG. 14B shows the resultsof the biodegradation portion of the ASTM D-6400 test performedaccording to ASTM D-5338 for sample 400. The results of thebiodegradation portion of the ASTM D-6400 test indicate that, after 180days, an amount of first polymeric material in samples 100, 300, and 400has degraded partially because the amount of carbon dioxide measured inthe test chamber is greater than the percentage of the starch-basedpolymeric material included in these samples. Thus, at least a portionof the remainder of the carbon dioxide emissions is due to thedegradation of the first polymeric material. This observation includessample 400, which is free of a biodegradation enhancing additive. Such aresult is surprising and advantageous. This example could be performedwith a “green” PE or other “green” polymeric material, and similarresults would be achieved.

TABLE 19 Sample Sample Sample Sample No. 100 No. 200 No. 300 No. 400Starch-Based Polymeric 30% 30% 40% 25% Material First Polymeric Material64% 15% 50% 70% Compatibilizer  5%  5%  5%  5% Biodegradation Enhancing 1%  1%  5%  0% Additive Second Polymeric Material  0% 49%  0%  0% FilmThickness (mm) 0.34 0.34 — 0.44 98 Day Biodegradability Results 33% 29%20% 22% 180 Day Biodegradability 55% 74% 45% 48% Results

Example 11

Three samples were tested for 349 days to determine biodegradabilitycharacteristics according to ASTM D-5511. The test was intended toreplicate the conditions of a full-scale anaerobic digester (landfill).The results of the three samples (referred to as 1342, 1343, and 1344)are shown in FIG. 15 and in Table 20. Sample 1342 was formed from 30%ESR (the starch-based polymeric material), 67% PBAT, and 3%compatibilizer, and had a thickness of 1.1 mil. Sample 1343 was formedfrom 27.5% ESR, 70% PBAT and 2.5% compatibilizer, and had a thickness of1.0 mil. Sample 1344 was formed from 40% ESR, 56% LLDPE and 4%compatibilizer, and had a thickness of 1.0 mil.

TABLE 20 Inoculum Negative Positive 1342 1343 1344 Cumulative Gas 4064.34898.8 12330.2 18429.0 20233.7 31171.1 Volume (mL) Percent CH₄ (%) 43.243.6 41.4 48.8 53.7 51.7 Volume CH₄ (mL) 1757.0 2135.1 5101.0 8992.610865.0 16106.6 Mass CH₄ (g) 1.26 1.53 3.64 6.42 7.76 11.5 Percent CO₂(%) 40.4 37.8 41.9 35.5 35.7 38.0 Volume CO₂ (mL) 1643.0 1852.9 5160.56547.5 7230.7 11838.7 Mass CO₂ (g) 3.23 3.64 10.14 12.86 14.20 23.25Sample Mass (g) 10 10 10 20.0 20.0 20 Theoretical 0.0 8.6 4.2 9.8 9.813.7 Sample Mass (g) Biodegraded 1.82 2.14 5.50 8.33 9.69 14.97 Mass (g)Percent 3.7 87.1 66.4 80.2 95.8 Biodegraded (%)

FIG. 15 shows that after 204 days, the negative control showed 2.5%degradation, the positive control showed 86.5% degradation, sample 1342showed 43.3% degradation, sample 1343 showed 53.9% degradation, andsample 1344 showed 77.2% degradation. At 349 days, the degradationvalues are as shown in Table 20.

The biodegradation after 349 days is particularly excellent. Forexample, while samples including PBAT (1342 and 1343) show very goodbiodegradation, with the percent biodegraded being far greater than thefraction of the starch-based polymeric material included in the film,sample 1344 is even more surprising, showing nearly 96% biodegradation(even higher than the positive control), where the non-starch-basedpolymeric material is polyethylene, which under normal circumstances isnot biodegradable (e.g., see the negative control, in Table 20 which was100% polyethylene). Such biodegradation results are remarkable, andparticularly advantageous. This example could be performed with a“green” PE, “green” PBAT, or other “green” polymeric material, andsimilar results would be achieved.

Example 12

Potato packaging bags made with a blend of 25% ESR, 70% LLDPE and 5%compatibilizer were tested for anaerobic biodegradation after 60 days,107 days, 202 days, 317 days, 439 days, 573 days, and 834 days accordingto ASTM D-5526. The test was intended to replicate the conditions of afull-scale anaerobic digester (landfill). The test was conducted undervarious conditions, with an inoculum having about 35%, 45%, and 60%organic solids with the balance being water. The results for theinoculum including 35% organic solids (and 65% water) are shown in FIG.16 and Table 21A. Table 21B shows results for other inoculum values, andfor other samples. The potato bags had a thickness of 1.35 mils. Thesebags are referred to as sample 1072.

TABLE 21A 35% 35% 35% 35% 35% 35% 35% Solids Solids Solids Solids SolidsSolids Solids @ 60 @ 107 @ 202 @ 317 @ 439 @ 573 @ 834 Days Days DaysDays Days Days Days 7.60% 11.80% 24.10% 39.40% 60.50% 71.70% 80.70%

The potato bags made with 25% ESR, and 70% LLDPE showed a remarkable 81%biodegradation over 834 days under simulated landfill conditions. TheESR is homogeneously blended with the polyethylene, and advantageouslyresults in the long carbon chains of the polyethylene being broken up,and digested by the same microorganisms that consume the starch-basedpolymeric ESR material. Such results show that the entire bag, includingthe polyethylene is being biodegraded into carbon dioxide, methane, andwater. Such results are surprising and particularly advantageous.

The testing conducted with 45% organic solids and 60% organic solidsalso showed results in which the percent of biodegradation exceeded thepercent of ESR included in the potato bag. Tests were also run withsimilar potato bags including 1% of a biodegradation enhancing additive(sample 1073), and other similar potato bags including Ecoflex®compostable resin, and metallocene LLDPE (sample 1075). This examplecould be performed with a “green” PE or other “green” polymericmaterial, and similar results would be achieved.

TABLE 21B Negative Control Positive Control Percent  60%  45%  35%  60% 45%  35% Solids Percent 1.20% 0.5% 1.5% 91.2% 91.2% 91.4% Biodegraded @834 days Sample 1072 Sample 1073 Percent  60%  45%  35%  60%  45%  35%Solids Percent 58.3% 67.7% 80.7% 54.5% 67.9% 80.3% Biodegraded @ 834days Sample 1075 Percent  60%  45%  35% Solids Percent 72.7% 83.3% 86.1%Biodegraded @ 834 days

Example 13

Films made with a blend of ESR and LLDPE were tested for anaerobicbiodegradation after 201 days and 370 days according to ASTM D-5338. Theconditions were meant to simulate aerobic digestion and/or industrialcompost conditions. The tested films are labeled 1345 and 1346 in Table22 and FIG. 17, which show the results after 370 days. At 201 days,samples 1345 and 1346 respectively showed adjusted percent biodegradedvalues of 74.2% and 72.4%, while the negative control showed −3.3% andthe positive control showed 100%. FIG. 17 plots actual % biodegradation.Sample 1345 included 25% ESR, 72.5% LLDPE, and 2.5% compatibilizer.Sample 1346 included 40% ESR, 56% LLDPE, and 4% compatibilizer. Bothfilms had a thickness of 1.0 mil. This example could be performed with a“green” PE or other “green” polymeric material, and similar resultswould be achieved.

TABLE 22 Inoc- Neg- Pos- ulum ative itive 1345 1346 Cumulative Gas3168.2 2864.3 10740.0 27603.3 24364.9 Volume (mL) Percent CO₂ (%) 81.482.6 83.5 89.3 87.8 Volume CO₂ 2577.8 2366.4 8965.3 24638.1 21400.0 (mL)Mass CO₂ (g) 5.06 4.65 17.61 48.40 42.04 Sample Mass (g) 1000 10 10 20.020.0 Theoretical 0.0 8.6 4.2 15.0 13.7 Sample Mass (g) Biodegraded 1.381.27 4.80 13.20 11.46 Mass (g) Percent −1.3 81.1 78.8 73.5 Biodegraded(%) Adjusted −1.6 100.0 97.2 90.7 Percent Biodegraded (%)

Example 14

Films made with a blend of ESR and PBAT were tested for anaerobicbiodegradation after 205 days according to ASTM D-6691, which is meantto simulate marine conditions. The tested films are labeled 1439 and1440 in Table 23 and FIG. 18. At 205 days, samples 1439 and 1440respectively showed adjusted percent biodegraded values of 49.6% and53.6%. Sample 1439 included 30% ESR, 67% PBAT, and 3% compatibilizer.Sample 1440 included 27% ESR, 70% PBAT, and 2.5% compatibilizer. Samplefilm 1439 had a thickness of 1.1 mil, and sample film 1440 had athickness of 1.0 mil.

TABLE 23 Inoc- Neg- Pos- ulum ative itive 1439 1440 Cumulative Gas 22.025.4 86.7 61.6 65.2 Volume (mL) Percent CO₂ (%) 91.8 85.4 88.7 91.7 91.3Volume CO₂ 20.2 21.7 76.9 56.4 59.5 (mL) Mass CO₂ (g) 0.040 0.043 0.1510.111 0.117 Sample Mass (g) 0.080 0.080 0.080 0.080 Theoretical 0.0690.034 0.039 0.039 Sample Mass (g) Biodegraded 0.011 0.012 0.041 0.0300.032 Mass (g) Percent 1.2 90.0 49.6 53.6 Biodegraded (%)

The films showed a greater degree of biodegradation over 205 daysrelative to the percentage of ESR included in the film. In other words,the long carbon chains of the polymer are being broken up, and digestedby the same microorganisms that consume the starch-based polymeric ESRmaterial. This example could be performed with a “green” PBAT or other“green” polymeric material, and similar results would be achieved.

Example 15

Additional manufactured films were tested for biodegradability. Table 24below summarizes the results of such testing, some of which aredescribed in detail above (e.g., Examples 13 and 14). Such testing showsexcellent biodegradability results across a wide range of fractions ofcarbohydrate-based polymeric materials, and different polymericmaterials, under various simulated conditions (e.g., landfills,composting, marine environments). These examples could be performed witha “green” PE, “green” PP, bioPET, “green” PBAT, or other “green”polymeric material, and similar results would be achieved.

TABLE 24 Sample Sample Sample Sample Sample Sample Sample MBR MBR MBRMBR MBR MBR 1072 16011801 15121706 16011801 16070601 15120101 15121703Test Landfill Landfill Compost Compost Compost Marine Marine ConditionASTM ASTM ASTM ASTM ASTM ASTM ASTM D-5526 D-5511 D-5338 D-5338 D-5338D-6691 D-6691 ESR % 25% 40% 25% 40% 40% 30% 27% Compati- 75% 60% 75% 60%11%  3%  3% bilizer + PE % PBAT %  0%  0%  0%  0% 49% 67% 70% Thickness1.35 mil 1 mil 1 mil 1 mil 1.5 mil 1 mil 1 mil Days 573 204 201 201 59205 205 % Degraded 71.1%  77.2%  74.2%  72.4%  96.9%  49.6%  53.6% 

Example 16

Films were manufactured from a blend of bio-polyethlene (sourced fromBraskem), ESR, and a Bynel® compatibilizer. Once formed, the resultingfilms were tested for dart strength (e.g., according to ASTM D-1709).Films were blown at various thicknesses, from 0.5 mil up to 2 mils, andat various percentages of a starch-based polymeric material (ESR)ranging from 0% to 35% ESR by weight. The results are shown in FIGS. 19Aand 19B.

As is apparent from FIG. 19A, the biopolyethyelene alone (no ESR)provides a dart strength of about 120 g for a thickness of 0.5 mil, adart strength of about 155 g for a thickness of 1 mil, a dart strengthof about 200 g for a thickness of 1.5 mils, and a dart strength of about270 g for a thickness of 2 mils. The approximate dart strengths areshown in Table 25A. Table 25B shows percentages of strength increases ascompared to the pure biopolyethylene film. It is readily apparent thatthere are increases for all thicknesses, and all tested percentages ofESR in the film. The increases in strength are particularly high as thefilms become thicker (i.e., the percentage increase is even moredramatic for thicker films as compared to thinner films).

TABLE 25A Dart Strength (g) ESR % 0.5 mil 1 mil 1.5 mils 2 mils  0% 120g 160 g 200 g 270 g 15% 165 g 225 g 290 g 385 g 25% 135 g 195 g 275 g395 g 35% 125 g 190 g 275 g 410 g

TABLE 25B Percent Increase in Dart Strength (%) ESR % 0.5 mil 1 mil 1.5mils 2 mils  0% — — — — 15% 38% 41% 45% 43% 25% 13% 22% 38% 46% 35%  4%19% 38% 70%

In forming and testing such films, Applicant observed that the resultsof increased strength generally match up well with the results seenusing synthetic petrochemical polyethylenes. As noted above, it wasobserved that when using the biopolyethylene material in the blend, theimprovement in strength increased more rapidly, as the thicknessincreased (i.e., the percentage increase is most dramatic for thickerfilms as compared to thinner films).

It was also observed that a sweetspot for starch-based ESR with thebiopolyethylene may be at about 15%, rather than the about 25% observedwith petrochemical sourced polyethylene. Nevertheless, increases instrength were similar observed when blending ESR with either base resin.

Finally, the films formed according to Example 16 include far more than40% biocontent, which is a particular advantage of the presentinvention, as both the base resin (e.g., any “green” sustainablepolymeric material such as those described herein) and thecarbohydrate-based or starch-based ESR material are derived fromsustainable materials. The only component in the films that did notcount towards biocontent is the compatibilizer (and where available, asustainable compatibilizer could conceivably be used). The biocontentmay thus be at least 40%, at least 45%, at least 50%, at least 55%, atleast 60%, at least 65%, at least 70%, at least 75%, at least 80%, atleast 85%, at least 90%, or even at least 95% by weight of the film orother product. The films of Example 16 consisted of biocontent, otherthan the Bynel® compatibilizer, such that they included greater than 90%biocontent by weight.

Finally, the films of Example 16 are substantially fully biodegradable,in a similar manner as described for the various other testedpolyethylenes of Examples 6-15. The present invention thus provides veryhigh biocontent polymer films and other products, which are not onlysustainable, but also biodegradable.

IV. Conclusion

In closing, although the various implementations have been described inlanguage specific to structural features and/or methodological acts, itis to be understood that the subject matter defined in the appendedrepresentations is not necessarily limited to the specific features oracts described. Rather, the specific features and acts are disclosed asexample forms of implementing the claimed subject matter.

In closing, it is to be understood that the embodiments of the inventivefeatures disclosed herein are illustrative of the principles of theinventive features. Other modifications that may be employed are withinthe scope of the inventive features. Thus, by way of example, but not oflimitation, alternative configurations of the inventive features may beutilized in accordance with the teachings herein. Accordingly, theinventive features are not limited to that precisely as shown anddescribed.

The invention claimed is:
 1. An article comprising: at least one ofbiopolyethylene or biopolypropylene; and a starch-based polymericmaterial configured to provide the at least one of biopolyethylene orbiopolypropylene with biodegradability, where the at least one ofbiopolyethylene or biopolypropylene itself is not otherwisesubstantially biodegradable; wherein the starch-based polymeric materialis formed from a plasticizer and one or more starches comprising one ormore of potato starch, corn starch or tapioca starch, the starch-basedpolymeric material has a crystallinity of less than about 20%, and doesnot re-form a crystalline structure, and has a water content of no morethan about 2%, and wherein the starch-based polymeric material and atleast one of biopolyethylene or biopolypropylene exhibit a substantiallack of sea-island features when blended together to form the article;wherein at least 25% of the biopolyethylene or biopolypropylenebiodegrades within 5 years under ASTM D-5511.
 2. The article of claim 1,wherein the at least one of biopolyethylene or biopolypropylenecomprises a biopolyethylene.
 3. The article of claim 2, wherein the atleast one of biopolyethylene or biopolypropylene is formed from one ormore of sugarcane or corn.
 4. The article of claim 1, wherein thestarch-based polymeric material is formed from two or more starches, afirst starch comprising one or more of potato starch, corn starch ortapioca starch, and a second starch comprising one or more of another ofpotato starch, corn starch or tapioca starch.
 5. The article of claim 4,wherein: an amount of the first starch comprises from about 50% to about90% by weight relative to a combined weight of the first starch and thesecond starch, and an amount of the second starch comprises from about10% to about 50% by weight relative to a combined weight of the firststarch and the second starch; and an amount of the starch-basedpolymeric material comprises from about 10% to about 40% by weight of acombined weight of the starch-based polymeric material and the at leastone of biopolyethylene or biopolypropylene, and an amount of the atleast one of biopolyethylene or biopolypropylene comprises from about60% to about 90% by weight of the combined weight of the starch-basedpolymeric material and the at least one of biopolyethylene orbiopolypropylene.
 6. The article of claim 5, wherein a strength of thearticle is at least about 5% greater than the article would have if madesolely from the at least one of biopolyethylene or biopolypropylene,without the starch-based polymeric material.
 7. The article of claim 1,wherein at least 90% of polymeric content of the article is sourced fromstarting materials which can be renewed within about 100 years or less.8. The article of claim 1, wherein the article comprises a film.
 9. Thearticle of claim 1, wherein the article comprises at least one of abottle or a sheet.
 10. An article comprising: biopolyethylene; and oneor more starch-based polymeric materials configured to provide thebiopolyethylene of the article with biodegradability, where thebiopolyethylene is not otherwise substantially biodegradable; whereinthe starch-based polymeric material is formed from a plasticizer and oneor more starches comprising one or more of potato starch, corn starch ortapioca starch, the starch-based polymeric material has a crystallinityof less than about 20%, and does not re-form a crystalline structure,and has a water content of no more than about 2%; wherein thestarch-based polymeric material and biopolyethylene exhibit asubstantial lack of sea-island features when blended together to formthe article; and wherein a strength of the article is at least about 5%greater than the article would have if made solely from thebiopolyethylene, without the starch-based polymeric material.
 11. Thearticle of claim 10, wherein the article comprises a film and has a dartdrop impact strength of at least about 100 g/mil of thickness.
 12. Thearticle of claim 10, wherein the biopolyethylene is formed from one ormore of sugarcane or corn.
 13. The article of claim 10, wherein thestarch-based polymeric material is formed from two or more starches, afirst starch comprising one or more of potato starch, corn starch ortapioca starch, and a second starch comprising one or more of another ofpotato starch, corn starch or tapioca starch.
 14. The article of claim13, wherein: an amount of the first starch comprises from about 50% toabout 90% by weight relative to a combined weight of the first starchand the second starch, and an amount of the second starch comprises fromabout 10% to about 50% by weight relative to a combined weight of thefirst starch and the second starch; and an amount of the starch-basedpolymeric material comprises from about 10% to about 40% by weight of acombined weight of the starch-based polymeric material and thebiopolyethylene, and an amount of the biopolyethylene comprises fromabout 60% to about 90% by weight of the combined weight of thestarch-based polymeric material and the biopolyethylene.
 15. The articleof claim 10, wherein a strength of the article is at least 10% greaterthan the article would have if made solely from the biopolyethylene,without the starch-based polymeric material.
 16. The article of claim10, wherein at least 90% of polymeric content of the article is sourcedfrom starting materials which can be renewed within about 100 years orless.
 17. The article of claim 10, wherein the article comprises a film.18. The article of claim 10, wherein the article comprises at least oneof a bottle or a sheet.
 19. The article of claim 1, further comprising acompatibilizer, wherein the compatibilizer is present in an amount of nomore than 8% by weight.
 20. The article of claim 10, further comprisinga compatibilizer, wherein the compatibilizer is present in an amount ofno more than 8% by weight.
 21. The article of claim 10, wherein astrength of the article is at least 20% greater than the article wouldhave if made solely from the biopolyethylene, without the starch-basedpolymeric material.
 22. An article comprising: PBAT; and a starch-basedpolymeric material configured to provide the PBAT with biodegradabilityunder ASTM D-6691; wherein the starch-based polymeric material is formedfrom a starch and a plasticizer, has a crystallinity of less than about20%, and does not re-form a crystalline structure, has a water contentof no more than about 2%, and the starch-based polymeric material andthe PBAT exhibit a substantial lack of sea-island features when blendedtogether to form the article; and wherein at least 25% of the PBATbiodegrades within 5 years under ASTM D-6691.
 23. The article of claim1, wherein the article is injection molded or extruded.
 24. The articleof claim 10, wherein the article is injection molded or extruded.
 25. Anarticle comprising: at least one of biopolyethylene or biopolypropylene;a starch-based polymeric material configured to provide the at least oneof biopolyethylene or biopolypropylene with biodegradability, where theat least one of biopolyethylene or biopolypropylene itself is nototherwise substantially biodegradable; and a compatibilizer, wherein thecompatibilizer is present in an amount of no more than 8% by weight;wherein the starch-based polymeric material is formed from a starch anda plasticizer, has a crystallinity of less than about 20%, and does notre-form a crystalline structure, and has a water content of no more thanabout 2%; wherein the starch-based polymeric material and at least oneof biopolyethylene or biopolypropylene exhibit a substantial lack ofsea-island features when blended together to form the article; whereinat least 25% of the biopolyethylene or biopolypropylene biodegradeswithin 5 years under ASTM D-5511.
 26. An article comprising:biopolyethylene; one or more starch-based polymeric materials configuredto provide the biopolyethylene of the article with biodegradability,where the biopolyethylene is not otherwise substantially biodegradable;and a compatibilizer, wherein the compatibilizer is present in an amountof no more than 8% by weight; wherein the starch-based polymericmaterial is formed from a starch and a plasticizer, has a crystallinityof less than about 20%, and does not re-form a crystalline structure,and has a water content of no more than about 2%; wherein thestarch-based polymeric material and biopolyethylene exhibit asubstantial lack of sea-island features when blended together to formthe article; wherein a strength of the article is at least about 5%greater than the article would have if made solely from thebiopolyethylene, without the starch-based polymeric material.
 27. Thearticle of claim 22, wherein the starch-based polymeric material isformed from one or more starches comprising one or more of potatostarch, corn starch or tapioca starch.
 28. The article of claim 22,wherein the starch-based polymeric material is formed from two or morestarches, a first starch comprising one or more of potato starch, cornstarch or tapioca starch, and a second starch comprising one or more ofanother of potato starch, corn starch or tapioca starch.
 29. The articleof claim 28, wherein: an amount of the first starch comprises from about50% to about 90% by weight relative to a combined weight of the firststarch and the second starch, and an amount of the second starchcomprises from about 10% to about 50% by weight relative to a combinedweight of the first starch and the second starch; and an amount of thestarch-based polymeric material comprises from about 10% to about 40% byweight of a combined weight of the starch-based polymeric material andthe PBAT, and an amount of the PBAT comprises from about 60% to about90% by weight of the combined weight of the starch-based polymericmaterial and the PBAT.
 30. The article of claim 22, wherein an amount ofthe starch-based polymeric material comprises from about 10% to about40% by weight of a combined weight of the starch-based polymericmaterial and the PBAT, and an amount of the PBAT comprises from about60% to about 90% by weight of the combined weight of the starch-basedpolymeric material and the PBAT.
 31. The article of claim 22, wherein atleast 90% of polymeric content of the article is sourced from startingmaterials which can be renewed within about 100 years or less.
 32. Thearticle of claim 22, wherein the article comprises a film.
 33. Thearticle of claim 22, wherein the article comprises at least one of abottle or a sheet.
 34. The article of claim 22, further comprising acompatibilizer, wherein the compatibilizer is present in an amount of nomore than 8% by weight.
 35. The article of claim 22, wherein the articleis injection molded or extruded.
 36. The article of claim 1, wherein anamount of the starch-based polymeric material comprises from about 10%to about 40% by weight of a combined weight of the starch-basedpolymeric material and the at least one of biopolyethylene orbiopolypropylene, and an amount of the at least one of biopolyethyleneor biopolypropylene comprises from about 60% to about 90% by weight ofthe combined weight of the starch-based polymeric material and the atleast one of biopolyethylene or biopolypropylene.
 37. The article ofclaim 10, wherein an amount of the starch-based polymeric materialcomprises from about 10% to about 40% by weight of a combined weight ofthe starch-based polymeric material and the biopolyethylene, and anamount of the biopolyethylene comprises from about 60% to about 90% byweight of the combined weight of the starch-based polymeric material andthe biopolyethylene.